AU2019201931A1 - Picolinamide compounds with fungicidal activity - Google Patents

Picolinamide compounds with fungicidal activity Download PDF

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AU2019201931A1
AU2019201931A1 AU2019201931A AU2019201931A AU2019201931A1 AU 2019201931 A1 AU2019201931 A1 AU 2019201931A1 AU 2019201931 A AU2019201931 A AU 2019201931A AU 2019201931 A AU2019201931 A AU 2019201931A AU 2019201931 A1 AU2019201931 A1 AU 2019201931A1
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compounds
mar
colorless oil
mmol
hydrogen
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AU2019201931B2 (en
Inventor
Karla BRAVO-ALTAMIRANO
Zachary BUCHAN
John Daeuble
Kyle DEKORVER
Jessica HERRICK
David Jones
Brian Loy
Yu Lu
Kevin Meyer
Jared RIGOLI
Xuelin Wang
Jeremy Wilmot
Chenglin Yao
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Corteva Agriscience LLC
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Dow AgroSciences LLC
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Priority to AU2021200664A priority patent/AU2021200664B2/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
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    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
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    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
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    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/20—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/52—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
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    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract

This disclosure relates to picolinamides of Formula I and their use as fungicides. Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. 5 Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less. Y' 0 R 1 R 11 R3 4

Description

PICOLINAMIDE COMPOUNDS WITH FUNGICIDAL ACTIVITY
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a divisional of Australian patent application no. 2015380298 and claims the benefit of U.S. Provisional Patent Application Serial Nos. 62/098120 filed December
30, 2014 and 62/098122 filed December 30, 2014, which are expressly incorporated by reference herein.
BACKGROUND & SUMMARY [0002] Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
[0003] The present disclosure relates to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
[0004] One embodiment of the present disclosure may include compounds of Formula 1:
Figure AU2019201931A1_D0001
J in which: X is hydrogen or C(O)Rs; 20 Y is hydrogen, C(O)Rs, or Q;
Q is
Figure AU2019201931A1_D0002
wherein: Z is Nor CH;
Ri is hydrogen or alkyl, each optionally substituted with 0, 1 or multiple FU; 25 R2 is methyl;
1002492809
2019201931 20 Mar 2019
R3 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple Rx;
R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy;
Rs is chosen from alkoxy or benzyl oxy, each optionally substituted with 0, 1, or multiple
Rs;
R6 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
R7 is chosen from hydrogen, -C(0)R9, or -CH2OC(0)R9;
Rs is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted with 0, 1, or multiple Rio;
R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple
Rs;
Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl;
Rn is chosen from hydrogen or alkyl, substituted with 0, 1, or multiple Rs;
R12 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple Rs.
[0004A] Another embodiment of the present disclosure may include a compound of
Formula 1 wherein:
X is hydrogen or C(O)Rs;
Y is hydrogen, C(O)R5, or Q; wherein: Z is N or CH:
Ri is hydrogen or alkyl, substituted with 0, 1 or multiple Rs;
R2 is methyl;
R3 is aryl optionally substituted with 0, 1 or multiple Rs, and bound to R12 either directly or through an oxo bridge;
R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy;
R5 is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple
Rs;
R6 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
R7 is chosen from hydrogen, -C(O)R9, or -CH2OC(O)R9;
Rs is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, each optionally substituted with 0, 1, or multiple Rio;
R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple
Rs;
1002492809
2019201931 20 Mar 2019
Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl;
Rn is chosen from hydrogen or alkyl, substituted with 0, 1 or multiple Rg; and R12 is aryl optionally substituted with 0, 1 or multiple Rs, and bound to R3 either directly or through an oxo bridge.
[0005] Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.
[0006] Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a 0 fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.
[0007] It will be understood by those skilled in the art that the following terms may include generic R-groups within their definitions, e.g., the term alkoxy refers to an -OR substituent. It is also understood that within the definitions for the following terms, these R groups are 5 included for illustration purposes and should not be construed as limiting or being limited by substitutions about Formula I.
[0008] The term alkyl refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
[0009] The term alkenyl refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.
[0010] The term alkynyl refers to a branched or unbranched carbon chain containing one 25 or more triple bonds including, but not limited to, propynyl, butynyl, and the like.
[0011] The terms aryl and Ar refer to any aromatic ring, mono- or bi-cyclic, containing 0 heteroatoms.
[0012] The term heterocyclyl refers to any aromatic or non-aromatic ring, mono- or bicyclic, containing one or more heteroatoms.
[0013] The term alkoxy refers to an -OR substituent.
[0014] The term acyloxy refers to an -OC(O)R substituent.
[0015] The term cyano refers to a -C=N substituent.
[0016] The term hydroxyl refers to an -OH substituent.
1002492809
2019201931 20 Mar 2019 [0017] The term amino refers to a -N(R)2 substituent.
[0018] The term arylalkoxy refers to -O(CH2)„Ar where n is an integer selected from the list 1,2, 3, 4, 5, or 6.
[0019] The term haloalkoxy refers to an -OR-X substituent, wherein X is CI, F, Br, or I, 5 or any combination thereof.
[0020] The term haloalkyl refers to an alkyl, which is substituted with CI, F, I, or Br or any combination thereof.
[0021] The term halogen or halo refers to one or more halogen atoms, defined as F, CI, Br, and I.
[0022] The term nitro refers to a -NO2 substituent.
[0023] The term thioalkyl refers to an -SR substituent.
[0024] Throughout the disclosure, reference to the compounds of Formula I is read as also including all stereoisomers, for example diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula I is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.
[0025] ft is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.
[0026] Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.
[0027] Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
[0027A] Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment, or any form of suggestion, that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art.
1002492809
2019201931 20 Mar 2019
DETAILED DESCRIPTION [0028] The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.
[0029] Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phyto logically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.
[0030] The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these
4A
2019201931 20 Mar 2019 compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
[0031] Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
[0032] Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2ethoxy ethanol.
[0033] Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
2019201931 20 Mar 2019 [0034] Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the //-butyl ether, ethyl ether or methyl ether of di ethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
[0035] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.
[0036] The compounds of Formula I can also be applied as granular formulations, which are 25 particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it 30 to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or
2019201931 20 Mar 2019 completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
[0037] Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
[0038] The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9- Cn alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (Ci2- Ci6) ethoxylate; di-.sttc-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) di oleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
[0039] The formulations may optionally include combinations that contain other pesticidal 25 compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different 30 pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.
2019201931 20 Mar 2019 [0040] The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces qitisqitalis, azaconazole, azoxystrobin, Bacillus suhtilis. Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), coumoxystrobin, cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dipymetitrone, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminostrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin 30 hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride,
2019201931 20 Mar 2019 mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metampotassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picarbutrazox, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triazoxide, triclopyricarb, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxyspontm, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (AS)-7V-(3,5-dichlorophenyl)-2-(methoxymethyl)succinimide, 1,2-dichloropropane, 1,3-dichloro-l, 1,3,3-tetrafluoroacetone hydrate, l-chloro-2,4dinitronaphthalene, l-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-l-yl)ethanol, 2,3dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5methylrhodanine, 4-(2-nitroprop-l-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, 25 barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril, benzamacrilisobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, di chi one, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim,
2019201931 20 Mar 2019 fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, 7/-3,5dichlorophenyl-succinimide, A-3-nitrophenylitaconimide, natamycin, A-ethylmercurio-4toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb, prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.
[0041] Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-di chloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, afidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, betacypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, broflanilide, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon 30 disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform
2019201931 20 Mar 2019 hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, clacyfos, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclaniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demetonS, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicloromezotiaz, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOCammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucofuron, flueycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprole, fluhexafon, flupyradifurone, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptafluthrin, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kappa-bifenthrin, kappa-tefluthrin, kelevan, kinoprene, lambda30 cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous
2019201931 20 Mar 2019 chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, momfluorothrin, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxy di sulfoton, paradichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyflubumide, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyriminostrobin, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tioxazafen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumezopyrim, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.
[0042] Additionally, the compounds described herein may be combined with herbicides that 30 are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and
2019201931 20 Mar 2019 synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, 30 epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam,
2019201931 20 Mar 2019 fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrione, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecopropP, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulluron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulluron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, or/Ao-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac,
2019201931 20 Mar 2019 quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vemolate, and xylachlor.
[0043] Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula
I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.
[0044] The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.
[0045] It will be understood by those skilled in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.
[0046] The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaeqitalis), powdery mildew of grapevine (Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice (Pyricularia oryzae), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodontm), powdery mildew of wheat (Blumeria graminis f. sp.tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Colletotrichum lagenarium), leaf spot of beet (Cercospora beticola), early blight of tomato (Alternaria solani), and spot blotch of
2019201931 20 Mar 2019 barley (Cochlioholus sativus). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
[0047] The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term disease-inhibiting and phytologically acceptable amount refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m2).
[0048] Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.
[0049] The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
GENERAL SCHEMES [0050] The following schemes illustrate approaches to generating picolinamide compounds 25 of Formula I. The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.
[0051] Compounds of Formula 1.1, wherein R3 and R12 are as originally defined and are equivalent, can be prepared by the methods shown in Scheme 1, step a. The compound of Formula 1.0 can be treated with an organometallic nucleophile such as phenylmagnesium bromide (PhMgBr) in a polar aprotic solvent such as tetrahydrofuran (THF) at a temperature of
2019201931 20 Mar 2019 about 0 °C to 23 °C to afford compounds of Formula 1.1, wherein R3 and Ri2 are as previously defined, as shown in a.
Figure AU2019201931A1_D0003
Figure AU2019201931A1_D0004
[0052] Compounds of Formula 2.2, wherein R3 is as originally defined and may or may not be equal to R32, can be prepared by the methods shown in Scheme 2, steps a - c. Compounds of Formula 2.2, wherein R3 and R|? are as previously defined but not an electron-deficient aryl or heteroaryl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.0, wherein R3 and R|? are as previously defined but not an electron-deficient aryl or heteroaryl group and may or may not be equivalent, with a mixture of a hydride reagent, such as triethylsilane (Et3SiH), and an acid, such as 2,2,2-trifluoroacetic acid (TFA) in a halogenated solvent such as di chloromethane (DCM) at a temperature of about 0 °C to 23 °C, as depicted in a. Alternatively, compounds of Formula 2.1, wherein R3 and R|? are an electron-deficient aryl or heteroaryl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.0, wherein R3 and R|? are an electron-deficient aryl or heteroaryl group and may or may not be equivalent, with a base, such as sodium hydride (NaH), and a catalyst, such as imidazole, in a polar aprotic solvent such as THF at a temperature of about 23 °C, followed by 20 sequential addition of carbon disulfide (CS2) and an alkyl iodide, such as iodomethane (Mel), as depicted in b. Compounds of Formula 2.2, wherein R3 and R|? are an electron-deficient aryl or heteroaryl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.1, wherein R3 and R|? are as previously defined and may or may not be equivalent, with a tin reagent, such as tributyltin hydride, and a radical initiator, such as 25 azobisisobutyronitriie (AIBN), in a nonpolar solvent such as toluene at a temperature of about 115 °C, as depicted in c.
Scheme 2
2019201931 20 Mar 2019
Figure AU2019201931A1_D0005
[0053] Compounds of Formula 3.1, wherein R3 and Ri2 are as originally defined and may or may not be equivalent, can be prepared according to the method outlined in Scheme 3, step a. Compounds of Formula 3.1, wherein R3 and R12 are as originally defined and may or may not be equivalent, can be prepared from compounds of Formula 3.0, wherein R3 and R12 are as previously defined and may or may not be equivalent, by treating with a base, such as NaH and an alkyl halide, such as Mel, in a polar aprotic solvent like A/A-dimethylformamide (DMF) at a temperature of about 0 °C to 23 °C, as depicted in a.
Figure AU2019201931A1_D0006
Figure AU2019201931A1_D0007
[0054] Compounds of Formula 4.1, wherein R3 and R12 are as originally defined and may 15 or may not be equivalent, can be prepared according to the method outlined in Scheme 4, step a. Compounds of Formula 4.1, wherein R3 and R12 are as originally defined and may or may not be equivalent, can be prepared from compounds of Formula 4.0, wherein R3 and R12 are as previously defined and may or may not be equivalent, by treating with a fluorination reagent, such as (diethylamino)sulfur trifluoride (DAST), in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as depicted in a.
2019201931 20 Mar 2019
Scheme 4
CH3
BnO
Figure AU2019201931A1_D0008
4.0 ch3
BnO
Figure AU2019201931A1_D0009
4.1 [0055] Compounds of Formula 5.3, wherein R3, R4, and R12 are as originally defined and R3 may or may not be equivalent to R12, can be prepared according to the methods outlined in Scheme 5, steps a - c. Compounds of Formula 5.3, wherein R3, R4, and R12 are as originally defined and R3 may or may not be equivalent to R42, can be prepared from compounds of Formula 5.0, wherein R3, R4, and R12 are as originally defined and R3 may or may not be equivalent to R12, by treating with a catalyst such as palladium on carbon (Pd/C) in a mixture of an unsaturated hydrocarbon solvent, such as cyclohexene, and a polar protic solvent, such as ethanol (EtOH), at an elevated temperature of about 65 °C, as shown in a. Alternatively, compounds of Formula 5.3, wherein R3 and R12 are an electron-deficient aryl or heteroaryl group and may or may not be equivalent and R4 is hydroxyl (OH) or alkoxy, can be obtained by treating compounds of Formula 5.1, wherein R3, R4, and R12 are as previously defined and R3 may or may not be equivalent to R12, with a mixture of a hydride reagent, such as Et3SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as indicated in b. Additionally, compounds of Formula 5.3, wherein R3 and R12 are as originally defined but not an electron-deficient aryl or heteroaryl group and may or may not be 20 equivalent, and R4 is a proton (H), can be obtained by treating the compounds of Formula 5.2, wherein R3, R4, and R|2 are as previously defined and R3 may or may not be equivalent to R42, with a mixture of a hydride reagent, such as Et3SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as depicted in c.
Scheme 5
2019201931 20 Mar 2019
BnO
CH,
Figure AU2019201931A1_D0010
R,
R-12 r4
5.0
PMBO
CH,
Figure AU2019201931A1_D0011
R,
R-12 r4
5.1
CH,
HO
Figure AU2019201931A1_D0012
R-I2
R4 r3
5.3
PMBO
CH,
Figure AU2019201931A1_D0013
R,
R-I2
OH
5.2 [0056] Compounds of Formula 6.2, wherein R3 and R12 are an electron-deficient aryl or heteroaryl group and equivalent, can be prepared according to the methods outlined in Scheme 6, steps a-b. Compounds of Formula 6.1, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 6.0, by treating with an aryl bromide, such as 4bromobenzonitrile, in the presence of a Pd catalyst, such as XPhos Pd G3 (CAS # 1445085-55-1, commercially available from Sigma-Aldrich), in a polar aprotic solvent such as THF at a tu temperature of about 55 °C, as indicated in a. Compounds of Formula 6.2, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 6.1, wherein R3 and R12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (A)-(+)-2-Methyl-CBS-oxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 0 °C, as indicated in b.
Scheme 6
Figure AU2019201931A1_D0014
6.0 6.1 6.2
2019201931 20 Mar 2019 [0057] Compounds of Formula 7.2, wherein R3 and R12 are as originally defined and equivalent, can be prepared according to the methods outlined in Scheme 7, steps a - h. Compounds of Formula 7.1, wherein R3 and R12 are as described previously, can be prepared from compounds of Formula 7.0, by treating with a catalyst, such as SbCl5, in a halogenated solvent such as DCM at a temperature of about 23 °C, as indicated in a. Compounds of Formula 7.2, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 7.1, wherein R3 and R12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (7?)-(+)-2-Methyl-CBSoxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 23 °C, as indicated in h.
Figure AU2019201931A1_D0015
Scheme 7
Figure AU2019201931A1_D0016
Figure AU2019201931A1_D0017
[0058] Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH2 or O, can be prepared according to the method outlined in Scheme 8, step a. Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH2 or O, can be prepared from compounds of Formula 8.0, wherein n is either 0 or 1, and W is either CH2 or O, by treating with a base, such as «-butyllithium (n-BuLi), and an aldehyde, such as acetaldehyde, in a polar aprotic solvent such as THF at a temperature of about -78 °C to 23 °C, as indicated in a.
Figure AU2019201931A1_D0018
Figure AU2019201931A1_D0019
2019201931 20 Mar 2019 [0059] Compounds of Formula 9.1, wherein R3 and R12 are as originally defined, can be prepared according to the method outlined in Scheme 9, step a. Compounds of Formula 9.1, wherein R3 and R12 are as originally defined, can be prepared from compounds of Formula 9.0, wherein R3is as originally defined (Formula 9.0 is either commerically available, or could be prepared from asymmetric Shi epoxidation of the corresponding /(-olefin precursor, as reported in Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc. 1997, 119, 11224), by treating with a pre-mixed suspension of a copper(I) salt, such as copper iodide (Cul), and an organometallic nucleophile, such as 4-(trifluoromethyl)phenylmagnesium bromide in a polar aprotic solvent such as THF, at a temperature of about -78 °C to 23 °C, as shown in a.
Scheme 9
H3c' ^r3 ch3
HO
9.0
9.1 [0060] Compounds of Formula 10.2, wherein Rb R2, R3, R4 and R12 are as originally defined, can be prepared according to the method outlined in Scheme 10, step a. Compounds of Formula 10.0, wherein R3 is as originally defined, can be treated with alcohols of Formula 10.1, wherein R2, R3, R4 and R12 are as originally defined, and a coupling reagent such as 3(ethyliminomethyleneamino)-7V,7V-dimethylpropan-l-amine hydrochloride (EDC), and a catalyst such as 7V,/V-dimethylpyridin-4-amine (DMAP) in a halogenated solvent like DCM to afford compounds of Formula 10.2, wherein Rb R2, R3, R4 and R|2 are as previously defined, as shown in a.
Figure AU2019201931A1_D0020
2019201931 20 Mar 2019 [0061] Compounds of Formula 11.2, wherein Rb R2, R3, R4, R6, R12 and Z are as originally defined, can be prepared according to the methods outlined in Scheme 11, steps a - b. As depicted in a, compounds of Formula 11.2, wherein Rb R2, R3, R4 and Ri2 are as originally defined, can be subjected to an acid, such as a 4 normal (N) solution of hydrogen chloride (HC1) in dioxane, in a halogenated solvent such as DCM to afford compounds of Formula 9.0, wherein Ri, R2, R3, R4 and Ri2 are as originally defined, as shown in a.
[0062] Compounds of Formula 11.0, wherein Rb R2, R3, R4 and Ri2 are as originally defined, can be treated with compounds of Formula 11.1, wherein R6 and Z are as originally defined, in the presence of a base, such as diisopropylethylamine (DIPEA), and a peptide coupling reagent, such as benzotriazol-l-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), in an halogenated solvent like DCM, to afford compounds of Formula 11.2, wherein Ri, R2, R3, R4, R45, R12 and Z are as originally defined, as shown in b.
Figure AU2019201931A1_D0021
Scheme 11
Figure AU2019201931A1_D0022
[0063] Compounds of Formula 12.0, wherein Ri, R2, R3, R4, R6, R7, R12 and Z are as originally defined, can be prepared according to the method outlined in Scheme 12, step a. As shown in a, compounds of Formula 11.2, wherein Rb R2, R3, R4, R6, R12 and Z are as originally defined, can be treated with an appropriate alkyl halide with or without a reagent such as sodium iodide (Nal) and an alkali carbonate base, such as sodium carbonate (Na2CC>3) or potassium
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2019201931 20 Mar 2019 carbonate (K2CO3), in a solvent like acetone at a temperature of about 55 °C, or by treatment with an acyl halide in the presence of an amine base, such as pyridine, triethylamine (Et3N), DMAP, or mixtures thereof, in an aprotic solvent such as DCM, at a temperature of about 23 °C, to afford compounds of Formula 12.0 wherein Rb R2, R3, R4, R6, R7, R12 and Z are as originally defined.
Scheme 12
Figure AU2019201931A1_D0023
11.2 12.0
EXAMPLES [0064] The chemistry in the following examples may be conducted using either enantiomer of 2-((/er/-butoxycarbonyl)amrno)propanoic acid (Boc-Ala-OH) or either protected (PMB or Bn) or unprotected enantiomer of ethyl lactate.
[0065] Example 1: Preparation of (5)-2-( benzyloxy)-1,1 -bis(4-fluorophenyl)propan-1 ol.
Figure AU2019201931A1_D0024
[0066] To a solution of (.S')-ethyl 2-(benzyloxy)propanoate (2.08 grams (g), 10.0 20 millimoles (mmol)) in tetrahydrofuran (THF; 20 milliliters (mL)) at 0 °C was slowly added (4fluorophenyl)magnesium bromide (31.3 mL, 25.0 mmol, 0.8 molar (M) in THF) over a 10 minute (min) period. The reaction vessel was allowed to warm slowly to room temperature over 2 hours (h), and the reaction mixture was quenched by careful addition of saturated (sat.) aqueous (aq.) ammonium chloride (NH4CI; 50 mL). The mixture was diluted with diethyl ether (Et2O; 50 mL),
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2019201931 20 Mar 2019 the phases were separated, and the aq. phase was extracted with Et2O (2 x 50 mL). The combined organic phases were washed with sat. aq. sodium chloride (NaCl, brine; 100 mL), dried over sodium sulfate (Na2SC>4), filtered, and concentrated. The resulting oil was purified by flash column chromatography (silica gel (SiO2), 0~>5% acetone in hexanes) to afford the title compound (3.28 g,
93%) as a colorless oil: NMR (300 MHz, CDC13) δ 7.47 - 7.38 (m, 2H), 7.38 - 7.27 (m, 5H),
7.17 - 7.09 (m, 2H), 7.04 - 6.89 (m, 4H), 4.64 (dd, J= 11.4, 0.7 Hz, 1H), 4.51 - 4.38 (m, 2H), 3.12 (s, 1H), 1.11 (d, 7=6.1 Hz, 3H); 19F NMR (376 MHz, CDC13) δ-116.19,-116.41; ESIMS m/z 377 ([M+Na]+).
[0067] Example 2A: Preparation of (5)-4,4'-(2-(benzyloxy)propane-1,1diyl)bis(fluorobenzene).
Figure AU2019201931A1_D0025
Figure AU2019201931A1_D0026
[0068] To a solution of (5)-2-(benzyloxy)-1,1 -bis(4-fluorophenyl)propan-1 -ol (709 milligrams (mg), 2.00 mmol) in dichloromethane (DCM; 20 mL) at 0 °C was added triethylsilane (Et3SiH; 3.19 mL, 20.0 mmol) followed by 2,2,2-trifluoroacetic acid (TFA; 1.53 mL, 20.0 mmol). The mixture was stirred at 0 °C for 1 h. The resulting solution was quenched by careful addition of sat. aq. sodium bicarbonate (NaHCO3; 20 mL). The phases were separated, and the aq. phase was extracted with DCM (2 x 30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2SC>4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (SiO2, 0-^ 10% acetone in hexanes) to afford the title compound (627 mg, 92%) as a white solid: 'H NMR (400 MHz, CDC13) δ 7.31 - 7.22 (m, 5H), 7.21-7.16 (m, 2H), 7.10 7.03 (m, 2H), 7.00-6.91 (m, 4H), 4.54 (dd,7= 11.5, 0.7 Hz, 1H),4.31 (dd, J= 11.6, 0.8 Hz, 1H), 4.14 (dq, 7= 8.1,6.1 Hz, 1H),3.93 (d,7=8.1 Hz, 1H), 1.18 (d, J= 6.0 Hz, 3H); 19FNMR(376
MHz, CDC13) δ -116.60, -117.10; ESIMS (m/z) 361 ([M+Na]+).
[0069] Example 2B: Preparation of (5)-(2-(benzyloxy)-1 -methoxypropane-1,1diyl)dibenzene.
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2019201931 20 Mar 2019
Figure AU2019201931A1_D0027
[0070] To a suspension of sodium hydride (NaH; 52.0 mg, 1.30 mmol, 60% weight per weight (w/w) in mineral oil) in Λζ/V-dimethylformamide (DMF; 3 mL) at 0 °C was added a solution of (>S)-2-(benzyloxy)-l,l-diphenylpropan-l-ol (318 mg, 1 mmol) in DMF (1 mL). The reaction mixture was stirred at room temperature for 30 min and then cooled to 0 °C. Iodomethane (Mel; 93.0 microliters (pL), 1.50 mmol) was added, and the reaction mixture was stirred at room temperature for 1 h. The resulting solution was quenched by careful addition of sat. aq. Nal ICCL, (10 mL). The mixture was diluted with diethyl ether (Et2O; 10 mL), the phases were separated, and the aq. phase was extracted with Et2O (2x10 mL). The combined organic phases were washed with brine (20 mL), dried over Na2SC>4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (SiO2, 0~>5% acetone in hexanes) to afford the title compound (295 mg, 89%) as a colorless oil: 'H NMR (400 MHz, CDC13) δ 7.47 - 7.41 (m, 2H), 7.40 - 7.35 (m, 2H), 7.33-7.18 (m, 11H), 4.69 (d, J= 11.9 Hz, 1H), 4.54 (d, J= 12.3 Hz, 1H), 4.50 (q,/= 6.1
Hz, 1H), 3.13 (s, 3H), 1.10 (d,/=6.1 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 142.96, 141.31, 138.79, 129.13, 128.54, 128.14, 127.61, 127.16, 127.08, 126.95, 126.69, 99.99, 85.35, 78.13,
70.80, 52.46, 13.65; ESIMS (m/z) 333 ([M+H]+).
[0071] diyl)dibenzene.
Example 2C: Preparation of (5)-(2-(benzyloxy)-l-fluoropropane-l,l-
Figure AU2019201931A1_D0028
[0072] To a solution of (5)-2-(benzyloxy)-l,l-diphenylpropan-l-ol (300 mg, 0.942 25 mmol) in DCM (5 mL) at 0 °C was added (diethylamino)sulfur trifluoride (DAST; 1.88 mL, 1.88 mmol, 1 M in DCM). The reaction was slowly warmed to room temperature over 3 h. The
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2019201931 20 Mar 2019 resulting solution was quenched by careful addition of sat. aq. Nal ICO, (5 mL). The phases were separated, and the aq. phase was extracted with DCM (2x10 mL). The combined organic phases were washed with brine (10 mL), dried over Na2SC>4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, OH 10% acetone in hexanes) to afford the title compound (300 mg, 98%) as a colorless oil: 'll NMR (400 MHz, CDCI3) δ 7.58 - 7.49 (m,
2H), 7.43 - 7.37 (m, 2H), 7.36 - 7.20 (m, 9H), 7.09 - 6.99 (m, 2H), 4.47 (d, J= 11.7 Hz, 1H), 4.37 -4.25 (m, 2H), 1.26 (dd, J= 6.3, 1.3 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 142.23 (d, J= 22.7 Hz), 141.00 (d,7= 23.5 Hz), 138.03, 128.21, 128.16, 127.90 (d,7= 1.5 Hz), 127.80, 127.72 (d,7= 1.7 Hz), 127.52, 127.42 (d,7= 1.3 Hz), 126.23 (d,7= 9.6 Hz), 125.93 (d,7= 8.7 Hz), 99.96 (d,7=
180.8 Hz), 78.91 (d, J= 26.9 Hz), 71.68, 14.47 (d, J= 3.6 Hz); 19FNMR(376 MHz, CDC13) δ159.80.
[0073] Example 2D, Step 1: Preparation of (5)-O-(2-(benzyloxy)-l,l-bis(3,4,5trifluorophenyl)propyl) .S'-methyl carbonodithioate.
Figure AU2019201931A1_D0029
Figure AU2019201931A1_D0030
[0074] To a solution of (5)-2-(benzyloxy)-l,l-bis(3,4,5-trifluorophenyl)propan-l-ol (496 mg, 1.16 mmol) in anhydrous THF (5.8 mL) was added NaH (93.0 mg, 2.33 mmol), followed by imidazole (3.96 mg, 0.0580 mmol), and the reaction mixture was stirred at ambient temperature for 1 h. Carbon disulfide (562 pL, 9.30 mmol) was added via syringe in one portion, followed by
Mel (579 pL, 9.30 mmol), and the reaction mixture was stirred at ambeint temperature for 2 h. The reaction mixture was diluted with Et20 (5 mL) and quenched with sat. aq. NH4CI (10 mL). The layers were separated, and the aq. layer was extracted with Et20 (3x10 mL). The combined organic layers were dried over magnesium sulfate (MgSCfi), filtered and concentrated to afford an orange/brown oil. The crude oil was purified by flash column chromatography (S1O2, 0H50% ethyl acetate (EtOAc) in hexanes) to afford the title compound (627 mg, 94%) as a clear, bright yellow colored oil: 'H NMR (400 MHz, CDC13) δ 7.40 - 7.27 (m, 3H), 7.24 - 7.16 (m, 2H), 7.02
1002492809
2019201931 20 Mar 2019 (dd, J= 9.1, 6.6 Hz, 2H), 6.96 (dd, J= 8.8, 6.5 Hz, 2H), 5.44 (q, J= 6.1 Hz, 1H), 4.66 (d, J= 11.6 Hz, 1H), 4.51 (d, J= 11.6 Hz, 1H), 2.49 (s, 3H), 1.16 (d, J = 6.1 Hz, 3H); 19F NMR (376 MHz, CDC13) δ -133.89 (d, 7 =20.7 Hz), -134.73 (d, J =20.6 Hz), -159.83 (t, J =20.6 Hz), -160.56 (t,7 = 20.7 Hz); (Thin film) 2922,1721,1622, 1595, 1526, 1436, 1344, 1241, 1217, 1197, 1119, 1088,
1040, 965, 908, 861, 822, 730, 712, 697, 672 cm1.
[0075] Example 2D, Step 2: Preparation of (5)-5,5'-(2-(benzyloxy)propane-1,1diy l)b is( 1,2,3 -trifluorobenzene).
Figure AU2019201931A1_D0031
[0076] A solution of (5)-<9-(2-(benzyloxy)-1,1 -bis(3,4,5-trifluorophenyl)propyl) 5methyl carbonodithioate (598 mg, 1.16 mmol) in toluene (200 mL) was degassed by a freezepump-thaw procedure (3 cycles using liquid nitrogen (N2)) under an atmosphere of N2. Tributyltin hydride (3.12 mL, 11.6 mmol) was then added, the reaction flask was fitted with a reflux condenser, and the reaction mixture was heated to a light reflux (115 °C). A solution of azobisisobutyronitrile (AIBN; 0.200 g, 1.22 mmol) in degassed toluene (3 cycles via liquid N2; 32 mL) was added via syringe down the reflux condenser over 3 h. Once slow addition of the AIBN was complete, the reaction mixture was stirred at reflux overnight. The solvent was removed in vacuo to provide a pale yellow oil. The crude oil was purified by flash column chromatography (S1O2, 0~>30% EtOAc in hexanes) to afford the title compound (358 mg, 72%) as a clear, colorless oil: 'H NMR (400 MHz, CDC13) δ 7.28 (d, J= 6.6 Hz, 3H), 7.17 - 7.06 (m, 2H), 6.92 (dd, J= 8.5, 6.5 Hz, 2H), 6.79 (dd, J= 8.3, 6.4 Hz, 2H),4.59 (d,7= 11.7 Hz, 1H), 4.31 (d, 7= 11.7 Hz, 1H), 4.02 (p, 7= 6.2 Hz, 1H), 3.76 (d,7=6.8Hz, 1H), 1.19 (d,7= 6.1 Hz, 3H); 19FNMR(376 MHz,
CDCh) δ-133.80 (d, 7= 20.5 Hz),
-134.34 (d, 7= 20.5 Hz), -162.54 (t,7= 20.5 Hz), -162.84 (t,7= 20.5 Hz); (Thin film) 2871,1621, 1526, 1445, 1345, 1262, 1235, 1116, 1096,1043, 859, 802, 728, 698, 679 cm1.
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2019201931 20 Mar 2019 [0077] Example 3A: Preparation of (5)-1,1 -bis(4-fluorophenyl)propan-2-ol.
Figure AU2019201931A1_D0032
Figure AU2019201931A1_D0033
[0078] To a solution of (5)-4,4'-(2-(benzyloxy)propane-l,l-diyl)bis(fluorobenzene) (575 mg, 1.70 mmol) in ethanol (EtOH; 11 mL) and cyclohexene (5.5 mL) at room temperature was added palladium on carbon (Pd/C; 362 mg, 0.0850 mmol, 2.5% w/w of Pd). The reaction mixture was stirred at 65 °C for 2 h, cooled to room temperature, filtered through a plug of Celite®, and concentrated to afford the title compound (415 mg, 98%) as a colorless oil: 'll NMR (400 MHz, CDC13) δ 7.36 - 7.29 (m, 2H), 7.25 - 7.18 (m, 2H), 7.09 - 6.93 (m, 4H), 4.47 (dqd, J= 8.2, 6.1,3.3 Hz, 1H), 3.80 (d, 7=8.3 Hz, 1H), 1.55 (d,7=3.3 Hz, 1H), 1.19 (d, 7= 6.1 Hz, 3H); 13C NMR (101 MHz, CDC13) δ 162.90 (d, 7= 23.3 Hz), 160.46 (d, 7 =23.1 Hz), 138.15 (d, 7= 3.1 Hz), 136.94 (d,7=3.6Hz), 130.14 (d,7= 7.8 Hz), 129.55 (d,7=7.8Hz), 115.70 (d,7= 18.8 Hz), 115.49 (d,7= 18.8 Hz), 70.07, 58.61,21.63; 19FNMR(376 MHz, CDC13) δ -115.84, -116.19.
[0079] Example 3B: Preparation of (5)-1,1 -bis(2-fluorophenyl)propane-1,2-diol.
Figure AU2019201931A1_D0034
[0080] To a solution of (5)-1,1-bis(2-fluorophenyl)-2-((4-methoxybenzyl)oxy)propan20 l-ol (790 mg, 2.06 mmol) in DCM (20 mL) at 0 °C was added Et3Si11 (3.28 mL, 20.6 mmol) followed by TFA (1.57 mL, 20.6 mmol). The mixture was stirred at 0 °C for 1 h. The resulting solution was quenched by careful addition of sat. aq. Nai ICO, (20 mL). The phases were separated, and the aq. phase was extracted with DCM (2x30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2SO4, fdtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, 0~> 10% acetone in hexanes) to afford the
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2019201931 20 Mar 2019 title compound (388 mg, 71%) as a colorless oil: 'll NMR (400 MHz, CDCfi) δ 7.90 - 7.77 (m, 1H), 7.70 (tt, J= 8.2, 1.5 Hz, 1H), 7.31-7.10 (m, 4H), 6.97 (ddd, J= 12.7, 8.1, 1.3 Hz, 1H), 6.88 (ddd, .7 = 11.8, 8.0, 1.4 Hz, 1H), 5.11 (qd, J= 6.3, 2.3 Hz, 1H), 3.49 (s, 1H),2.27 (s, 1H), 1.09 (d,J = 6.3 Hz, 3H); 19F NMR (376 MHz, CDCfi) δ -112.90 (d, J= 8.3 Hz), -113.92 (d, J= 8.4 Hz);
ESIMS (m/z) 551 ([2M+Na]^).
[0081] Example 3C: Preparation of (5)-1,1 -bis(4-bromophenyl)propan-2-ol.
Figure AU2019201931A1_D0035
Figure AU2019201931A1_D0036
[0082] To a solution of (5)-1,1 -bis(4-bromophenyl)-2-((4-methoxybenzyl)oxy)propanl-ol (1.80 g, 3.56 mmol) in DCM (18 mL) at 0 °C was added Et3SiH (5.68 mL, 35.6 mmol) followed by TFA (2.72 mL, 35.6 mmol). The mixture was warmed slowly to room temperature over 3 h. The resulting solution was quenched by careful addition of sat. aq. Nal ICO3 (20 mL).
The phases were separated, and the aq. phase was extracted with DCM (2 x 30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2SC>4, filtered, and concentrated.
The resulting oil was purified by flash column chromatography (S1O2, 0-^ 10% acetone in hexanes) to afford the title compound (742 mg, 56%) as a colorless oil: 'H NMR (300 MHz, CDCfi) δ 7.51 - 7.36 (m, 4H), 7.25 - 7.17 (m, 2H), 7.18 - 7.06 (m, 2H), 4.48 (dq, J= 8.2, 6.1 Hz, 1H), 3.76 (d, J = 8.2 Hz, 1H), 2.80 (s, 1H), 1.19 (d, J= 62 Hz, 3H); 13CNMR(75 MHz, CDCfi) δ 140.94,
139.85, 131.98, 131.85, 130.39, 129.84, 121.06, 120.72,69.82,58.91,21.65; (Thin film) 3390,
3024, 2969, 2900, 1486, 1072 cm1.
[0083] Example 3D, Step 1: Preparation of (5)-1,1 -bis(4-((trimethylsilyl)ethynyl)phenyl)propan-2-ol.
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2019201931 20 Mar 2019
Figure AU2019201931A1_D0037
[0084] To a solution of (5)-1 ,l-bis(4-bromophenyl)propan-2-ol (1.01 g, 2.72 mmol) in THF (9 mL) was added bis(triphenylphosphine)palladium dichloride (0.095 g, 0.136 mmol) and 5 copper(I) iodide (Cul; 0.026 g, 0.136 mmol). The mixture was sparged with N2 for 20 min, and triethylamine (ΕίβΝ; 4.53 mL) was added dropwise. To the resulting mixture was added ethynyltrimethylsilane (El5 mL, 8.15 mmol) dropwise, and the mixture was heated to reflux and stirred overnight. The mixture was cooled to room temperature, and the reaction was quenched with sat. aq. Nal IC'Cf. The products were extracted with EtOAc (2x), and the combined organic 0 layers were washed with brine, dried over Na2SO4, filtered and concentrated. The crude residue was then purified by flash column chromatography (S1O2, 0~>20% acetone in hexanes) to provide the title compound (495 mg, 45%) as a brown foam: 'll NMR (400 MHz, CDCI3) δ 7.48 - 7.42 (m, 2H), 7.42 - 7.37 (m, 2H), 7.33 - 7.27 (m, 2H), 7.24 - 7.17 (m, 2H), 4.51 (dqd, J= 12.2, 6.1, 3.5 Hz, 1H), 3.81 (d, 7=8.3 Hz, 1H), 1.60 (d, 7= 3.8 Hz, 1H), 1.18 (d, 7= 6.1 Hz, 3H), 0.26 (s,
9H), 0.26 (s, 9H); 13CNMR(101 MHz, CDC13) δ 142.55, 141.48, 132.42,132.29, 128.69, 128.15,
121.90, 121.57, 104.76, 104.71, 94.49, 94.33, 69.76, 59.96,21.55, 0.00; (Thin film) 3397, 2960, 2156, 1501, 1248, 861, 840 cm1; HRMS-ESI (m/z) [M+H]+ calcd for C25H33OSi2, 405.2064; found, 405.2070.
[0085] Example 3D, Step 2: Preparation of (5)-1,1 -bis(4-ethynylphenyl)propan-2-ol.
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2019201931 20 Mar 2019
Figure AU2019201931A1_D0038
[0086] To a solution of (5)-1 ,l-bis(4-((trimethylsilyl)ethynyl)phenyl)propan-2-ol (0.470 g, 1.16 mmol) in methanol (MeOH; 5.8 mL) was added potassium carbonate (K2CO3; 0.482 g,
3.48 mmol). The mixture was stirred for 1 h at room temperature and then filtered through Celite®.
The filter cake was washed with MeOH, and the filtrate was concentrated. The crude material was purified by flash column chromatography (S1O2, 0-^20% acetone in hexanes) to provide the title compound (288 mg, 95%) as a yellow oil: 'll NMR (300 MHz, CDCI3) δ 7.48 - 7.43 (m, 2H), 7.43 -7.39 (m, 2H), 7.35-7.29 (m, 2H), 7.24-7.19 (m, 2H), 4.51 (dqd, J= 8.3, 6.1, 3.7 Hz, 1H), 3.82 (d, 7=8.3 Hz, 1H), 3.05 (s, lH),3.04(s, 1H), 1.63 - 1.55 (m, 1H), 1.18 (d,7= 6.1 Hz, 3H); 13C
NMR (101 MHz, CDC13) δ 142.84, 141.82,132.60, 132.48, 128.74, 128.22, 120.87, 120.57, 83.31, 83.29, 77.39, 77.29, 69.73, 59.96, 21.66; (Thin film) 3436, 3280,2968, 2106,1499, 1075, 825 cm '; HRMS-ESI (m/z) [M+H]+ calcd for Ci9Hi7O, 261.1274; found, 261.1272.
[0087] Example 3D, Step 3: Preparation of (5)-1,1 -bis(4-ethylphenyl)propan-2-ol.
Figure AU2019201931A1_D0039
[0088] To a solution of (5)-l,l-bis(4-ethynylphenyl)propan-2-ol (0.144 g, 0.553 mmol) in EtOAc (2.8 mL) was added palladium (5% weight (wt) on carbon, dry basis; 0.235 g, 0.055 mmol). The mixture was stirred under a balloon of hydrogen overnight. The mixture was filtered
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2019201931 20 Mar 2019 through Celite®, and the filter cake was washed with EtOAc. The combined filtrate was then concentrated, and the crude residue was purified by flash column chromatography (SiO2, 0->25% acetone in hexanes) to provide the title compound (97.0 mg, 65%) as a clear oil: 'll NMR (400 MHz, CDC13) δ 7.33 - 7.25 (m, 2H), 7.22 -7 .15 (m, 2H), 7.18 - 7.11 (m, 2H), 7.10 (d, J= 8.1 Hz,
2H), 4.51 (dqd, 7= 8.7, 6.1, 2.5 Hz, 1H), 3.74 (d, J= 8.9 Hz, 1H), 2.65-2.53 (m, 4H), 1.68 (d, 7=
2.8 Hz, 1H), 1.23- 1.14 (m, 9H); 13CNMR(101 MHz, CDC13) δ 142.74, 142.33, 139.94, 138.91, 128.48, 128.40, 128.07, 128.02, 70.19, 60.02, 28.41, 28.39,21.37, 15.47, 15.46; (Thin film) 3421, 2963, 1510, 1110, 821 cm1; HRMS-ESI (m/z) ([M+Na]+) calcd for Ci9H24NaO, 291.1719; found, 291.1725.
[0089] Example 3E: Preparation of I -(9/7-xanthen-9-yl(ethanol.
Figure AU2019201931A1_D0040
[0090] To a solution of 977-xanthene (364 mg, 2.00 mmol) in THF (10 mL) at -78 °C 5 was added n-butyllithium (2.5 M in hexanes; 0.880 mL, 2.20 mmol). The mixture was stirred at 78 °C for 30 min. Acetaldehyde (0.226 mL, 4.00 mmol) was added, and the reaction mixture was warmed slowly to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. NH4C1 (10 mL). The phases were separated, and the aq. phase was extracted with Et2O (2x15 mL). The combined organic phases were washed with brine (20 mL), dried over
Na2SO4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (SiO2, 0-> 10% acetone in hexanes) to afford the title compound (216 mg, 48%) as a colorless oil: 'H NMR (400 MHz, CDC13) δ 7.33 - 7.22 (m, 4H), 7.17 - 7.04 (m, 4H), 3.99 (d, J= 5.1 Hz, 1H), 3.96-3.82 (m, 1H), 1.54 (d,7=6.0Hz, 1H), 1.00 (d, 7=6.3 Hz, 3H); 13CNMR(101 MHz, CDCh) δ 152.94, 152.65, 129.54, 129.30, 128.19, 128.17, 123.18, 123.14, 122.48, 121.73,116.59,
116.41, 73.07, 47.06, 18.81; ESIMS (m/z) 475 ([2M+Na]+).
[0091] Example 3F: Preparation of (15,25)-1-phenyl-1-(4(trifluoromethyl)phenyl)propan-2-ol.
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Figure AU2019201931A1_D0041
[0092] To a mixture of magnesium turnings (102 mg, 4.20 mmol) in Et20 (4 mL) was added l-bromo-4-(trifluoromethyl)benzene (0.588 mL, 4.20 mmol) at room temperature, followed by Mel (5 pL). Upon warming to a gentle boil using a heat gun, the mixture turned a yellow/brown color. The reaction was then stirred in a water bath at room temperature for 30 min until almost all the magnesium was consumed. This was added to a suspension of copper(I) iodide (Cul; 400 mg, 2.10 mmol) in Et20 (4 mL) at -78 °C. The reaction was stirred at -20 °C for 30 min, then cooled to -78 °C, and (21S',35)-2-methyl-3-phenyloxirane (0.201 mL, 1.50 mmol) was added. The resulting mixture was warmed slowly to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. NH4CI (10 mL). The phases were separated, and the aq. phase was extracted with Et20 (2x15 mL). The combined organic phases were washed with brine (20 mL), dried over Na2SO4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, 0-^ 10% acetone in hexanes) to afford the title compound (390 mg, 94%) as a light yellow oil: 'H NMR (400 MHz, CDC13) δ 7.60 - 7.50 (m, 2H), 7.48 - 7.38 (m, 2H), 7.38
-7.33 (m, 4H), 7.30-7.23 (m, 1H), 4.58 (dqd, J= 8.4, 6.1, 3.5 Hz, 1H), 3.88 (d, J= 8.5 Hz, 1H), 1.65 (d, J= 3.6 Hz, 1H), 1.20 (d, J= 6.1 Hz, 3H); 19FNMR(376 MHz, CDCI3) δ -62.49; ESIMS (m/z) 263 ([M-0H]+).
[0093]
Example 3G, Step 1: Preparation of 4,4'-(2-oxopropane-l,l-diyl)dibenzonitrile.
Figure AU2019201931A1_D0042
[0094] To a suspension of 4-bromobenzonitrile (546 mg, 3.00 mmol) and cesium carbonate (977 mg, 3.00 mmol) in THF (10 mL) under anN2 atmosphere was added acetone (1.10 mL, 15.00 mmol), followed by X-Phos Pd G3 (50.8 mg, 0.060 mmol). Then, the vial was sealed and heated to 55 °C for 4 days. The reaction was diluted with EtOAc (30 mL) and washed with sat.
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NH4CI (3x10 mL), water (15 mL), and brine (15 mL). Then the organic phase was dried over Na2SC>4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, 0-^40% EtOAc in hexanes) to afford the title compound (174 mg, 22%) as a colorless oil: 'H NMR (400 MHz, CDC13) δ 7.66 (d, J= 8.4 Hz, 4H), 7.34 (d, J= 8.3 Hz, 4H), 5.21 (s, 1H), 2.29 (s,3H); 13CNMR(101 MHz, CDC13) δ 203.68, 142.15, 132.75, 129.64, 118.21, 112.00,64.25,
30.43; ESIMS m/z 261 ([M+H]+).
[0095] Example 3G, Step 2: Preparation of (.9)-4,4'-(2-hydroxypropane-1,1diyl)dibenzonitrile.
Figure AU2019201931A1_D0043
Figure AU2019201931A1_D0044
[0096] To a solution of 4,4'-(2-oxopropane-l,l-diyl)dibenzonitrile (174 mg, 0.668 mmol) in toluene (4.5 mL) was added (R)-l-methyl-3,3-diphenylhexahydropyrrolo[l,2c][l,3,2]oxazaborole (1 M solution in toluene, 66.8 pL, 0.067 mmol). Then, the reaction was cooled to 0 °C and a solution of BH3-DMS (69.8 μΐ, 0.735 mmol) in 0.5 mL toluene was added over 2 min. The flask was left to stir at 0 °C. After 2 h, the reaction was quenched with methanol (0.5 mL), diluted with EtOAc and added water. Phases were separated and the aqueous phase was extracted with EtOAc x 2. The combined organic phases were washed with brine (20 mL), dried over Na2SO4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, 0-^50% EtOAc in hexanes) to afford the title compound (99.7 mg, 57%) as a colorless oil: JH NMR (400 MHz, CDC13) δ d 7.60 (dd, J = 8.4, 6.8 Hz,
4H), 7.51 - 7.46 (m, 2H), 7.43 - 7.37 (m, 2H), 4.63 - 4.47 (m, 1H), 3.97 (d, J= 7.5 Hz, 1H), 1.97 (d, 7=3.8 Hz, 1H), 1.21 (d, 7=6.2 Hz, 3H).13C NMR (101 MHz, CDC13) δ 146.91, 145.86, 132.60, 132.45, 129.90, 129.19, 118.58, 118.51, 110.96, 110.92, 69.19,59.56,22.27; ESIMS m/z 263 ([M+H]+).
[0097] Example 3H, Step 1: Preparation of 3,3-diphenylbutan-2-one.
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Figure AU2019201931A1_D0045
[0098] To a magnetically stirred mixture of 2,3-diphenylbutane-2,3-diol (500 mg, 2.06 mmol) in DCM (10 mL) was added antimony pentachloride (26.5 pL, 0.206 mmol) under air atmosphere. The reaction mixture was stirred at 25 °C for 1 h and then was quenched by slow addition of sat. aq. Nal ICO,. The resulting mixture was diluted with water and additional DCM, and the organic layer was separated by passing through a phase separator. The resulting oil was purified by flash column chromatography (S1O2, 0-^5% acetone in hexanes) to afford the title compound (330 mg, 71 %) as a colorless oil: 'H NMR (400 MHz, CDCI3) δ 7.36 - 7.31 (m, 4H), 7.30 - 7.25 (m, 2H), 7.23 - 7.15 (m, 4H), 2.11 (s, 3H), 1.87 (s, 3H); 13C NMR (101 MHz, CDC13) δ 209.16, 143.59,128.36,126.91, 62.32, 27.62, 26.42; ESIMS m/z 225 ([M+H]+).
[0099] Example 3H, Step 2: Preparation of (5)-3,3-diphenylbutan-2-ol.
Figure AU2019201931A1_D0046
[00100] To a solution of 3,3-diphenylbutan-2-one (150 mg, 0.669 mmol) in toluene (4.5 mL) was added (7?)-l-methyl-3,3-diphenylhexahydropyrrolo[l,2-c][l,3,2]oxazaborole (1 M solution in toluene, 134 pL, 0.134 mmol). Then, a solution of BH3-DMS (70.2 pL, 0.702 mmol) in 0.5 mL of toluene was added to the reaction mixture over 2 min. The flask was left to stir at room temperature. After 1 h, the reaction was quenched with methanol (0.5 mL). DCM and water were added, and the phases were separated. The aqueous phase was extracted with DCM (2x). The combined organic phases were washed with brine (20 mL), dried over Na2SO4, filtered, and concentrated. The resulting oil was purified by flash column chromatography (S1O2, 0-^20% acetone in hexanes) to afford the title compound (150 mg, 99%) as a colorless oil: 'll NMR (400 MHz, CDCI3) δ d 7.39 - 7.17 (m, 1 OH), 4.70 - 4.61 (m, 1H), 1.67 (s, 3H), 1.51 (d, 7= 4.9 Hz, 1H), 1.11 (d, J =6.3 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 147.30, 145.86, 128.40, 128.15,128.05, 127.79, 126.20, 126.01, 72.28, 51.77, 23.26, 18.39; ESIMS m/z 227 ([M+H]+).
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1,2-diol.
Example 31, Step 1: Preparation of (5)-1 ,l-bis(2,3-dimethoxyphenyl (propane-
Figure AU2019201931A1_D0047
[00102] To a solution of isopropylmagnesium lithium chloride (1.3 M in THF, 6.1 mL, 8.00 mmol) was added THF (2 mL) and l-bromo-2,3-dimethoxybenzene (1.74 g, 8.00 mmol). The resulting brown solution was heated to a gentle reflux (75 °C external temp) for 2.5 h, then cooled to 0 °C in an ice water bath. (5)-methyl 2-hydroxypropanoate (0.191 ml, 2 mmol) was then added dropwise via syringe. The reaction was stirred at 0 °C for 1 h, then removed from the cold bath and stirred overnight at rt. The reaction was cooled to 0 °C in an ice water bath, diluted with water (20 mL), brine (20 mL), and Et2O (40 mL), and was quenched with 1 N HC1 (8 mL). The phases were separated, and the aqueous phase was extracted with Et2O (20 mL). The organic phases were combined, dried over MgSCfi, filtered, and concentrated to provide an oil. Purification by automated silica gel column chromatography (5-50% EtOAc in hexanes) provided the title compound (568 mg, 82%) as a yellow, crystalline solid: 'll NMR (300 MHz, CDCfi) δ 7.43 (td, J = 8.0,1.5 Hz, 2H), 7.11 (td, J= 8.1, 4.9 Hz, 2H), 6.83 (dd, J= 8.1, 1.4 Hz, 2H), 5.06-4.82 (m,
1H), 4.74 (d, J= 1.2 Hz, 1H), 3.81 (s, 3H), 3.80 (s, 3H), 3.20 (s, 3H), 3.04 (s, 3H), 2.86 (d, J= 9.5 Hz, 1H), 0.97 (d, J= 6A Hz, 3H); 13C NMR (126 MHz, CDCfi) δ 152.89, 152.82, 146.94, 145.53, 139.56, 138.92, 123.32, 123.26, 122.01, 119.01, 111.30, 79.20, 77.22, 60.07, 59.26, 55.77, 55.64, 18.34; HRMS-ESI (m/z) ([M+Na]') calcd for Ci9H24O6Na, 371.1465; found, 371.1456.
[00103]
Example 31, Step 2: Preparation of l,l-bis(2,3-dimethoxyphenyl)propan-2-one.
Figure AU2019201931A1_D0048
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2019201931 20 Mar 2019 [00104] To a solution of (5)-1,l-bis(2,3-dimethoxyphenyl)propane-l,2-diol (560 mg,
1.61 mmol) in anhydrous CH2CI2 (8 mL) at 0 °C was added triethylsilane (770 pi, 4.82 mmol) and trifluoroacetic acid (TFA, 124 pL, 1.61 mmol). The resulting solution was stirred at 0 °C for 2 h, then removed from the cold bath and stirred for 2 h. TFA (248 pL, 3.2 mmol) was added, and the reaction was then stirred overnight at rt. The reaction was diluted with water (25 mL) and extracted with CH2CI2 (3x 25 mL). The organic extracts were dried over Na2SC>4, filtered, and concentrated to provide an oil. Purification by automated silica gel column chromatography (5-25% acetone in hexanes) provided the title compound (396 mg, 75%) as a white solid: 'll NMR (300 MHz,
CDCI3) δ 6.99 (t, J= 8.0 Hz, 2H), 6.87 (dd, J= 8.2, 1.5 Hz, 2H), 6.67-6.54 (m, 2H), 5.86 (s, 1H),
3.87 (s, 6H), 3.75 (s, 6H), 2.25 (s, 3H); 13CNMR (126 MHz, CDC13) δ 207.18, 152.69, 147.02,
132.23, 123.74,121.61, 111.64, 60.36, 55.74, 51.96, 29.80; HRMS-ESI (m/z) ([M+Na]+) calcd for Ci9H22O5Na, 353.1359; found, 353.1353.
[00105] Example 31, Step 3: Preparation of l,l-bis(2,3-dimethoxyphenyl)propan-2-ol.
Figure AU2019201931A1_D0049
[00106] To a solution of l,l-bis(2,3-dimethoxyphenyl)propan-2-one (356 mg, 1.08 mmol) in methanol (3.5 mL) was added sodium borohydride (61 mg, 1.6 mmol). The resulting solution was stirred at rt for 20 h, then was quenched with sat'd NH4CI (1 mL), diluted with water (20 mL) and extracted with CH2CI2 (3x 20 mL). The organic extracts were combined, dried over
Na2SC>4, filtered, and concentrated to provide the title compound (360 mg, 100%) as an oil: 'll
NMR (300 MHz, CDC13) δ 7.16-6.88 (m, 4H), 6.79 (ddd, J= 9.6, 7.8, 1.9 Hz, 2H), 4.81 (d, J= 8.3 Hz, 1H), 4.53 - 4.32 (m, 1H), 3.84 (s, 3H), 3.84 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H), 2.04 (d, J= 4.2 Hz, 1H), 1.22 (d, J= 62 Hz, 3H); 13CNMR(126 MHz, CDC13) δ 152.98, 152.83, 147.71, 147.04, 136.17, 135.33, 123.94, 123.62, 120.96, 120.84, 110.76, 110.48, 70.32,60.26, 60.20,
55.66, 55.63, 45.11, 21.80; IR (neat film) 3451, 2935, 2833, 1582, 1473, 1428, 1266,1215, 1167,
1125, 1088, 1068, 1004, 964, 908, 835, 809, 787, 748, 728.
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2019201931 20 Mar 2019 [00107] Example 4A: Preparation of (5)-(5)-1,1 -diphenylpropan-2-yl 2-((tertbutoxycarbonyl)amino)-propanoate.
BocHN
Figure AU2019201931A1_D0050
BocHN
Figure AU2019201931A1_D0051
[00108] To a solution of (5)-1,1 -diphenylpropan-2-ol (317 mg, 1.493 mmol) in DCM (15 mL) at 0 °C were added (5)-2-((/er/-butoxycarbonyl)amino)propanoic acid (Boc-Ala-OH; 311 mg, 1.64 mmol) and .V,.V-dimethylpyridin-4-amine (DMAP; 18.2 mg, 0.149 mmol) followed by N -((ethylimino)methylene)-.V ,N -dimethylpropane-1,3-diamine hydrochloride (EDC; 573 mg, 2.99 mmol), and the reaction mixture was stirred at room temperature overnight and concentrated to give a yellow oil. The crude material was purified by flash column chromatography (SiCL,
->10% acetone in hexanes) to afford the title compound (433 mg, 75%) as a colorless oil: 'll NMR (400 MHz, CDC13) δ 7.42 - 7.07 (m, 1 OH), 5.80 (dq, J= 10.1,6.1 Hz, 1H), 4.97 (d, 5=8.0 Hz, 1H), 4.19-4.06 (m, 1H), 4.03 (d,5= 10.1 Hz, 1H), 1.41 (s, 9H), 1.23 (d,5= 6.1 Hz, 3H), 0.76 (d, 5= 7.2 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 172.83, 154.96, 141.52, 141.26, 128.79,
128.50, 128.10,128.08, 126.91, 126.67, 79.62, 73.10, 57.98, 49.21, 28.33, 19.31, 17.98; ESIMS m/z 384 ([M+H]4).
[00109] Example 5, Step 1: Preparation of (5)-1 -(((5)-1,1 -diphenylpropan-2-yl)oxy)-1 oxopropan-2-aminium chloride.
Figure AU2019201931A1_D0052
Figure AU2019201931A1_D0053
[00110] To a solution of (5)-(5)-1,1 -diphenylpropan-2-yl 2-((/er/butoxycarbonyl)amino)propanoate (Cmpd 2; 433 mg, 1.13 mmol) in DCM (6 mL) was added a 4 N solution of HC1 in dioxane (2.8 mL, 11.3 mmol), and the mixture was stirred for 3 h at room temperature. The solvent was evaporated under a stream of N2 to provide the title compound (360 mg, 100%) as a white solid: ESIMS (m/z) 284 ([M+H]4).
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2019201931 20 Mar 2019 [00111] Example 5, Step 2: Preparation of (5)-(5)-1,1 -diphenylpropan-2-yl 2-(3hydroxy-4-methoxypicolinamido)propanoate.
Figure AU2019201931A1_D0054
Figure AU2019201931A1_D0055
[00112] To a solution of (5)-1-(((.3)-1,1 -diphenylpropan-2-yl)oxy)-1-oxopropan-2aminium chloride (Cmpd 46; 361 mg, 1.13 mmol) and 3-hydroxy-4-methoxypicolinic acid (210 mg, 1.24 mmol) in DCM (11 mL) were added benzotriazol-l-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP; 646 mg, 1.24 mmol) and .V-ethyl-iV-isopropylpropan-2-amine (DIPEA; 0.651 mL, 3.72 mmol), and the reaction mixture was stirred for 2 h at room temperature.
The solvent was evaporated and the crude oil was purified by flash column chromatography (SiO2,
Ά50% acetone in hexanes) to afford the title compound (340 mg, 70%) as a white foam: 'll NMR (400 MHz, CDCI3) δ 12.10 (s, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.38 7.06 (m, 10H), 6.86 (d, J= 5.3,1H), 5.83 (dq, J= 10.1, 6.1 Hz, 1H), 4.52 (dq, J= 8.1, 7.2 Hz, 1H), 4.06 (d, J= 10.2 Hz, 1H), 3.93 (s, 3H), 1.26 (d, J= 6.1 Hz, 3H), 0.97 (d, J= 7.2 Hz, 3H); 13C
NMR (101 MHz, CDC13) δ 171.67, 168.53, 155.34, 148.72, 141.38, 141.13,140.40, 130.48,
128.80, 128.50, 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93, 56.07, 47.85, 19.24, 17.61; HRMS ESI (m/z) ([M+H]+) calcd for C25H27N2O5, 435.1920; found, 435.1925.
[00113] Example 6A: Preparation of (5)-(5)-l,l-diphenylpropan-2-yl 2-(3-acetoxy-420 methoxypicolinamido)propanoate.
Figure AU2019201931A1_D0056
[00114] To a solution of (5)-(5)-1,1 -diphenylpropan-2-yl 2-(3-hydroxy-4methoxypicolinamido)-propanoate (Cmpd 90; 70.0 mg, 0.161 mmol), Et2N (44.9 pL, 0.332
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2019201931 20 Mar 2019 mmol), and DMAP (3.94 mg, 0.032 mmol) in DCM (3.2 mL) was added acetyl chloride (17.2 pL, 0.242 mmol) at room temperature, and the reaction mixture was stirred for 2 h. The solvent was evaporated, and the resulting crude oil was purified by flash column chromatography (SiCE,
->40% acetone in hexanes) to afford the title compound (75.0 mg, 97%) as a colorless oil: 'll
NMR (400 MHz, CDC13) δ 8.41 (d, J= 7.8 Hz, 1H), 8.30 (d, J= 5.4 Hz, 1H), 7.38 - 7.10 (m,
10H), 6.97 (d, J= 5.4 Hz, 1H), 5.82 (dq, J= 10.0, 6.2 Hz, 1H), 4.52 (dt, J= 8.2, 7.1 Hz, 1H), 4.05 (d, J= 10.1 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.24 (d, J= 6.1 Hz, 3H), 0.89 (d, J= 7.1 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 172.23, 168.89,162.28, 159.42,146.66, 141.55, 141.44, 141.25, 137.45, 128.77, 128.50, 128.13, 128.11, 126.89, 126.67, 109.73,73.32, 57.90, 56.27,47.85,20.75,
19.25,17.92; HRMS ESI (m/z) ([M+H]+) calcd for C27H29N2O6,477.2025; found, 477.2019.
[00115] Example 6B: Preparation of (5)-(5)-l,l-diphenylpropan-2-yl 2-(3(acetoxymethoxy)-4-methoxypicolinamido)propanoate.
Figure AU2019201931A1_D0057
[00116] To a suspension of (5)-(5)-l,l-diphenylpropan-2-yl 2-(3-hydroxy-4methoxypicolinamido)-propanoate (Cmpd 90; 100 mg, 0.230 mmol) and K2CO3 (63.6 mg, 0.460 mmol) in acetone (4.6 mL) was added bromomethyl acetate (33.9 pL, 0.345 mmol) at room temperature, and the mixture was heated to 55 °C for 3 h and then cooled to room temperature. The solvent was evaporated and the resulting crude material was purified by flash column chromatography (S1O2, 1 Ά40% acetone in hexanes) to afford the title compound (94.0 mg, 80% yield) as a colorless oil: JH NMR (400 MHz, CDC13) δ 8.25 (d, J= 5.4 Hz, 1H), 8.22 (d, J= 7.9 Hz, 1H), 7.34-7.09 (m, 10H), 6.92 (d, J= 5.4 Hz, 1H), 5.83 (dq, J= 10.1, 6.2 Hz, 1H), 5.72 (d, J = 0.7 Hz, 2H), 4.60-4.49 (m, 1H), 4.06 (d, J= 10.1 Hz, 1H), 3.88 (s, 3H), 2.05 (s, 3H), 1.25 (d, J =6.1 Hz, 3H), 0.91 (d, J= 7.2 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 172.33,170.25,162.88,
160.24, 145.70, 143.91, 142.54, 141.48, 141.25, 128.76, 128.49, 128.12, 128.09, 126.89,126.65,
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109.56, 89.50, 73.27, 57.92, 56.17, 48.07, 20.86, 19.25, 17.73; HRMS-ESI (m/z) [M+H]+ calcd for C28H3iN2O7, 507.2131; found, 507.2125.
[00117] Example 6C: Preparation of (5)-(5)-1,1 -diphenylpropan-2-yl 2-(35 ((isobutyryloxy)methoxy)-4-methoxypicolinamido)propanoate.
Figure AU2019201931A1_D0058
[00118] To a solution of (5)-(5)-1,1 -diphenylpropan-2-yl 2-(3-hydroxy-4methoxypicolinamido)-propanoate (Cmpd 90; 100 mg, 0.230 mmol) in acetone (4.6 mL) were added sodium carbonate (Na2CO3; 73.2 mg, 0.690 mmol), sodium iodide (Nal; 6.90 mg, 0.046 mmol) and chloromethyl 2-ethoxyacetate (62.9 mg, 0.460 mmol). The mixture was heated to 55 °C overnight and then cooled to room temperature, and the solvent was evaporated. The resulting residue was purified by flash column chromatography (SiO2, 2->30% acetone in hexanes) to afford the title compound (79.0 mg, 64%) as a colorless oil: 'll NMR (400 MHz, CDC13) δ 8.28 (d, J=
7.9 Hz, 1H), 8.25 (d, J= 5.3 Hz, 1H), 7.36 - 7.08 (m, 10H), 6.92 (d, J= 5.4 Hz, 1H), 5.83 (dq, J=
10.1,6.2 Hz, 1H), 5.79-5.69 (m, 2H), 4.62-4.44 (m, 1H),4.O6 (d,7= 10.1 Hz, 1H), 3.86 (s,
3H), 2.53 (hept,7= 7.0 Hz, 1H), 1.25 (d,7= 6.2 Hz, 3H), 1.13 (d, 7= 7.0 Hz, 6H), 0.91 (d,7= 7.2 Hz, 3H); 13CNMR(101 MHz, CDC13) δ 176.22, 172.34, 162.85, 160.23, 145.55, 144.16, 142.18, 141.48, 141.26, 128.76, 128.49, 128.12, 128.09, 126.89, 126.65, 109.48, 89.90, 73.26, 57.93,
56.12,48.07, 33.85, 19.26, 18.68, 17.74; HRMS-ESI (m/z) ([M+H]4) calcd for C30H35N2O7,
535.2444; found, 535.2431.
[00119] Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Zymoseptoria tritici; Bayer code SEPTTR):
[00120] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water (H2O) containing 110 ppm Triton X-l 00. The fungicide solutions were
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2019201931 20 Mar 2019 applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases, unless stated otherwise. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the 5 fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.
[00121] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soiE50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either 0 prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. When disease symptoms were fully expressed on the 1st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent 5 disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.
[00122] Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia recondita f. sp. tritici; Bayer code PUCCRT):
[00123] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soiE50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22 °C with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
[00124] Example C: Evaluation of Fungicidal Activity: Wheat Glume Blotch (Leptosphaeria nodorum; Bayer code LEPTNO):
[00125] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soiE50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per
1002492809
2019201931 20 Mar 2019 pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 h after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 5 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
[00126] Example D: Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer code VENTIN):
[00127] Apple seedlings (variety McIntosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 h after fungicide treatment and kept in a 22 °C dew chamber with 100% relative humidity for 48 h, and then moved to a greenhouse set at 20 °C for disease to develop.
Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00128] Example E: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer code CERCBE):
[00129] Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 h after fungicide treatments. Inoculated plants were kept in a dew chamber at 22 °C for 48 h then incubated in a greenhouse set at 24 °C under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00130] Example F: Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi·, Bayer code PHAKPA):
[00131] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of H2O containing 0.011% Tween 20. The fungicide solutions were applied 30 onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.
1002492809
2019201931 20 Mar 2019 [00132] Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22 °C and 100% relative humidity then transferred to a growth room at 23 °C for disease to 5 develop. Disease severity was assessed on the sprayed leaves.
[00133] Example G: Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis', Bayer code RHYNSE):
[00134] Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when the first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22°C with 100% relative humidity for 48 h. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves 5 followed the procedures as described in the Example A.
[00135] Example H: Evaluation of Fungicidal Activity: Rice Blast (Pyricularia oryzae', Bayer code PYRIOR):
[00136] Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 h after fungicide treatments.
After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00137] Example I: Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani', Bayer code ALTESO):
[00138] Tomato plants (variety Outdoor Girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22 °C for
1002492809
2019201931 20 Mar 2019 disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00139] Example J: Evaluation of Fungicidal Activity: Cucumber Anthracnose (Colletotrichum lagenarium', Bayer code COLLLA):
[00140] Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
2019201931 20 Mar 2019
Table 1. Compound Structure, Preparation Method, and Appearance
*Cmpd. No. Structure Prepared According To Example Appearance
1 0 CHo Η II 1 OH SyYWF 0 CH3 0 ch3 Example 1; Example 3A; Example 4A White Solid
2 0 CH3 YyWY J CH3 0 CH3 Example 1; Example 2A; Example 3A; Example 4A Colorless Oil
3 0 CH3 S-N ϊυΥ'Λ'Υ'7 5 ch3 0 ch3 Λ \ s Example 1; Example 2A; Example 3A; Example 4A Colorless Oil
4 0 CH3 |< YyVA+J 5 ch3 o ch3 F Example 1; Example 2A; Example 3A; Example 4A Clear, Colorless Oil
5 0 CH3 γγ/γυ 3 ch3 o ch3 Example 1; Example 2B; Example 3A; Example 4A Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H 0 ch3 II I Example 1;
H3CL XX /N„, Example
6 h3c¥ ¥ ( Ύ 0 2B; Colorless Oil
ch3 0 ch3 Yh3 Example 3A;
Example 4A
o CH3 ¥
HAT ¥ ¥.j Example 1;
h CY ¥ r Example 2A;
7 CHq 0 CHq K ¥» Colorless Oil
Ti ¥ Example
3A;
Example 4A
F
H 0 ch3 II 1 AA Example 1;
H3C, ,0. .N,„ Example
8 H3C^f V '< o ¥< ¥ 2C; Colorless Oil
CH3 0 ch3 G Example
r ¥ 3A;
A Example 4A
. Λ
C Η I ch3 G Y CH3 Example 1;
H3C. .0. .N,„ ¥ J
h3c¥ ¥ i o Example
9 ch3 0 ch3 A 2A; Example Colorless Oil
AG 3A;
Example 4A
ch3
F
0 ch3 Example 1;
H II T Example
10 H3C 0 N,„ h3c¥ Π Ά τ' -AG 2A; Example Colorless Oil
ch3 0 CH3 3A;
il Example 4A
A. G
F v
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
11 Cl 0 CH3 ΦΫΛν J ch3 0 ch3 /k Cl Example 1; Example 2A; Example 3A; Example 4A Colorless Oil
12 o ch3 ΦΫΛνχ 0 ch3 0 ch3 Example 3E; Example 4A Colorless Oil
13 0 CH3 η;οΥου·ΛοΛ?τ CH3 0 CH3 Example 3E; Example 4A Colorless Oil
14 0 CH3 [^ |< ΦΥ-Λ¥ 0 ch3 0 ch3 Br Example 1; Example 3C; Example 4A Colorless Oil
15 ch3 o ch3 s-^ ch3 0 ch3 A <ζ s ch3 Example 1; Example 3C; Example 4A Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
16 /CH3 0 CH3 jy/AA 0 ch3 0 ch3 Jx ch3 Example 1; Example 2A; Example 3A; Example 4A Colorless Oil
18 F o ch3 0 ch3 0 ch3 A. Example 3F; Example 4A Colorless Oil
19 /Cl 0 CH3 ϊ+γ’ΝΝ 0 ch3 0 ch3 Cl Example 1; Example 2A; Example 3A; Example 4A Colorless Oil
20 0 CH3 ch3 0 ^k F Example 1; Example 2A; Example 3A; Example 4A Clear Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
21 YY Y 0 CH3 ch3 o J h3c Q F Example 1; Example 2A; Example 3A; Example 4A Clear Oil
22 o ch3 Y |Y Y/AA ch3 ο Y /k h3c ch3 Y j F Example 1; Example 2A; Example 3A; Example 4A Clear Oil
23 /W Y 0 CH3 Y |< YyWA ' CH3 0 k^CH3 X. ch3 y F Example 1; Example 2A; Example 3A; Example 4A Clear Oil
24 ch3 l J o. o ch3YY Yy’AW CH3 0 CH3 .0. L CH3 Example 1; Example 3C; Example 4A Sticky Wax
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
25 h3c^ 0 0 CH3 J ch3 0 ch3 A. JU /CH3 Example 1; Example 3C; Example 4A Sticky Wax
26 F /CH3 0 CH3 jy/AW J ch3 0 ch3 A. ^^F ch3 Example 1; Example 3C; Example 4A Sticky Wax
27 Cl /CH3 0 CH3 0 ch3 o ch3 JL ch3 Example 1; Example 3C; Example 4A Sticky Wax
28 ^CH o ch3 ΪυΥ'ΛΎ^ 0 ch3 0 ch3 J. CH Example 1; Example 3C; Example 3D, Steps 1-2; Example 4A White Foam
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
29 0 CH3 YYcH3 ΪυΥ'ΛΆ 0 ch3 0 ch3 A. ^ch3 Example 1; Example 3C; Example 3D, Steps 1-3; Example 4A Sticky Wax
31 o ch3 !Ζγ¥Λ-υ J ch3 o ch3 Example 3F; Example 4A Clear Oil
33 /^ /Cl 0 CH3 |Z V H3C. JD. -N,, JL h3c 1 II 1 oh 3 ch3 0 ch3 Cl Example 1; Example 3B; Example 4A White Solid
34 0 CH3 V <cvY·/(AM, 3 ch3 0 ch3 Cl Example 1; Example 3B; Example 4A White Solid
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
xCI
0 CH3 ri Y\/
xCH3 Example 1; Example 2A;
35 ch3 0 ch3 White Solid
As Example
3A;
M Example 4A
Cl
F
0 h3c, am ^n„ X. ch3 Ά Yl
Χγ, JJ Example 1;
36 η 7Y Y r ο^γ Yh Example White Foam
ch3 0 ch3 F\ 3B;
Example 4A
A
F F
0 Η II ch3 Example 1;
H3C. JY /N/z, A Χγ Example
37 γτ Y Yo ch3 0 ch3 2A; Clear,
Example Colorless Oil
3A;
^F Example 4A
F
Cl F
0 Η || ch3 Example 1;
h3c. CX .n,„ Example
38 H3cY Y r 0 2A; Clear,
ch3 0 ch3 Example Colorless Oil
3A;
Yl Example 4A
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
ch3
/k /F
H 0 ch3 II 1 F ik Example 1;
H3C. .ChN ,,, Ύ/Η Example
39 H3cY Y ch3 0 2A; Clear,
CH3 /L Example Colorless Oil
3A;
yh3 Example 4A
F
H3C. XX -N,„ 0 ch3
Yk l| Example 1;
h c¥ Y 1 cr ^Y Example
40 J ch3 0 ch3 .Y 2A; White Foam
1 Example
kY 3A;
Example 4A
γΊι
o ch3 YX/
H HX AX X , A PJ Jk Example 1;
h3c^T V Example 2A;
43 ch3 0 CH3 /k White Solid
r il Example
3A;
ΧχΥ Yl Example 4A
Cl
/\ /Cl
0 ch3 X |<
H3C 0 N, h3cHT Π Uk Example 1; Example 2A;
44 ch3 0 ch3 X. White Solid
r i Example
3A;
lyy X Example 4A
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
45 0 CH3 II I OH Η2Ν,,Λ02γν C, Example 5, Step 1 White Solid
46 0 CH3 h2n„.. CH3 (fS Example 5, Step 1 Colorless Oil
47 ch3 \ s Example 5, Step 1 Colorless Oil
48 /F 0 CH3 |1^ h2n,„ CHs X F Example 5, Step 1 Pale Yellow Oil
49 0 CH3 h2n,,,X0XAJ ch3 <7~V°'^Ch3 Example 5, Step 1 Colorless Oil
50 0 CH3 r^>i H2N%,.lJyV CH3 Example 5, Step 1 Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
51 F\ /F 0 CH3 |< h2n„, AoAA/ CHs A/ F Example 5, Step 1 Colorless Oil
52 0 CH3 CH3 T/ Example 5, Step 1 Colorless Oil
53 0 CH3 ch3 H2N„,^orJU chs /L h3c Example 5, Step 1 Colorless Oil
54 F o ch3 h2n,„ CH3 X. Example 5, Step 1 Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
Cl
0 I I ch3 <iil
55 Example 5, Step 1 Colorless Oil
ch3 [Γί
cr
0 ch3
56 ha/0 ch3 ίΓη Example 5, Step 1 Colorless Oil
0 ch3
57 H2N-/o ch3 A° Example 5, Step 1 Colorless Oil
/Br 0 CH3 / |X
H2N„...A J
58 I ch3 Γί Example 5, Step 1 Colorless Oil
Br
ch3
0 11 ch3 s Λ
59 ch3 Example 5, Step 1 Colorless Oil
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
0 I I CH3 Al· /CH3
h2n,,„ A
60 Γ ch3 Example 5, Step 1 Colorless Oil
ch3
0 ch3 Λχ
H2N/ AAJ
61 ch3 ί^Ν Example 5, Step 1 White Solid
ί^Ν
F >F
0 I I CH3
63 h2n,,„ X oA-M Example 5, Step 1 Colorless Oil
ch3
0 ch3 .Cl
H2N„, A -AX
64 I ch3 Example 5, Step 1 Colorless Oil
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
ch3
Ox 0 ch3 x
65 II 1 Example 5, Step 1 Sticky Oil
CH3 Jx ch3
h3® 0
0 ch3 x
66 ΗΑ..^θΓ. -J Example 5, Step 1 Sticky Oil
CH3 -x
ch3
F
0 ch3 Αγ· /CH3
67 CH3 -X X® Example 5, Step 1 Sticky Oil
^F
ch3
Cl
o CH3 r II 1 ° /CH3
68 CH3 X. X/ Example 5, Step 1 Sticky Wax
kJ ^Cl
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
0 CHq x>CH /A-
h2n„ Λ
69 I ch3 X Example 5, Step 1 Sticky Wax
X 1 ( 1 :h
0 I I ch3 ^ch3
h2n„, X
70 ch3 X Example 5, Step 1 Sticky Wax
X xch3
o ch3 Xs F
71 Example 5, Step 1 White Solid
F
0 ch3 Xs F
H2N,,„ JV
72 c 'CH3 r aX Example 5, Step 1 White Solid
/X
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
0 ch3 XF
H*A
73 T h3c ch3 Example 5, Step 1 White Solid
J
F
0 ch3 F
h2n„ 2
74 h3c^J Example 5, Step 1 White Solid
ch3
F
0 ch3 A /F
75 H2N/-px^O' ch3 Example 5, Step 1 White Solid
0 I I ch3 /Cl
77 H2N--^O' ch3 OH XCI Example 5, Step 1 White Solid
T3I
Cl
0 ch3 r^^Tr /Cl
78 «/-o' ch3 OH XF Example 5, Step 1 White Solid
T
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
o ch3 II 1 XCI
79 H2N CH3 JL Me Example 5, Step 1 White Solid
Cl
80 F\ 0 CH3>^>r H2N,,„ XzCV 1 ΓΌΗ ch3 Cl ^Cl Example 1; Example 3B; Example 4A; Example 5, Step 1 Sticky Oil
F 0 ch3 II 1
81 Η2Ν/'·|^^ο'χ^χγ CH3 f^I Oh Example 5, Step 1 Sticky Oil
K o chX O\
83 h2n,, 1 XoH CH3 Example 5, Step 1 Colorless Oil
T
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
F
0 ch3 i^TF
84 h2n„, A ch3 O' Example 5, Step 1 Clear, Colorless Oil
Ax
F
Cl
0 ch3 .y
85 h2Nz, A ch3 O' AA Example 5, Step 1 Clear, Colorless Oil
Ax
F
ch3
0 ch3 r¥F
86 h2n„ A ch3 O' AA Example 5, Step 1 White Solid
Αχ ^ch3
F
0 ch3 ΠΓα
87 H2N,,„ A ch3 Ox AA, Example 5, Step 1 White Solid
Ax ^Cl
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
88 ++ XI 0 CH3 A jA h2n„,.,^oX>^f CHs Cl Example 5, Step 1 White Solid
89 /CH3 0 ++ /OH ++ n o ch3 An Η II I OH 0 ch3 Example 5, Step 2 White Solid
90 Η’% (7x+0H o CH3 UN o ch3 JL fl Ί Example 5, Step 2 White Foam
91 H3C^ 0 +J+ /OH A 7< o ch3 s^\ H II f / v N ' 0 ch3 1 As Example 5, Step 2 Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H>-0 1 .OH yy /F
0 ch3 y y
H II 1
92 γ'Ά' ¥¥¥¥ Example 5, White Foam
0 ch3 Step 2
/¥
F
+f'o 1 .OH
¥ o CH3 ¥¥]
93 L ¥^n/z„ A X AyJ Example 5, White Foam
N Π I 0 Step 2
II 1 0 ch3 Α°η
ί| | £h3
H>'0 ¥ .OH
¥ o CH3 ¥¥
95 L A A AJ Example 5, Colorless Oil
N Π 1 0 Step 2
II 1 0 ch3 1 °¥H3
(l Ί
HjC'o .OH ¥ /F
0 ¥ rV
H II 1
¥ ¥ . .N,z ¥\ / ¥^¥y>¥ Example 5,
96 N White Foam
0 ch3 yL /F Step 2
¥ ¥
¥¥
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 0
97 V kx N OH R,y ch3 'Ό/χ/ yy. Example 5, Step 2 Colorless Oil
0 ch3
\zA
h3c% O
98 OH O CH, o ch3 ii A yy /°X y ch3 Example 5, Step 2 Colorless Oil
H3cA°
H3(\ 0 F
99 4 N,J ch3 yy Example 5, Step 2 Colorless Oil
0 ch3
H3C^ 0 Cl
100 V kx N OH N,J ch3 o^y yy Example 5, Step 2 Colorless Oil
O ch3
cr
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c^ 0 .OH
o CH3
101 5L/N,,„ A Example 5, Colorless Oil
N Π 1 0 Step 2
o ch3
ΙΐΊ
+% 1 .OH
r 0 CH3 Υφ
102 C. X Example 5, Colorless Oil
N Y I 0 Step 2
0 ch3 yL /0
ίι
h3c^ 0 .OH .Br
0 CH, Y Y
H II ,
Y Λ \/%z Example 5,
103 N YY |^° Colorless Oil
o ch3 Step 2
Χί
Br
h3y 0 .oh ch3
γΛι id s ch3 s-X
104 Y Y N γ ''·φ^0ζ Example 5, Step 2 Colorless Oil
o ch3 Χέ
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 3 0
6 -0H 0 H II ch3 A /CH3
105 kk ΎΫ 0 ch3 Y A/AA flY Ay ch3 Example 5, Step 2 Colorless Oil
106 H3C'O ό -0H 0 w ck NO Example 5, Step 2 Colorless Gel
0 ch3
Ay
H3Cx 0
A ΌΗ Y o H II ch3 γ Cl
107 ks N SfN//T o ch3 xo A/A A Ay Cl Example 5, Step 2 Colorless Gel
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
109 H3C^ /^x 0 x π /k /OH Ax, ΓΓ h u ΐ3 nr^ O CH3 J, Example 5, Step 2 Colorless Oil
110 /OH /^/F ΠΓ « Π3 Γϊ 0 ch3 A^ F Example 5, Step 2 Clear, Colorless Oil
111 h3c^o A, /OH /^/F π η ? Γ3 Γϊ o CH3 Jx j} F Example 5, Step 2 Clear, Colorless Oil
112 /^ /OH /^/F Ah Π3 ΓΓ νγΝ,.^·0Λ>/ o CH3 Jx j} F Example 5, Step 2 Clear, Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
1 ΌΗ F
kY < 0 ch3
113 M 9/, Example 5, White Solid
11 0 •s Step 2
Y/
F
H3C^ 0 /OH F
kY < o ch3 kY
H II
k> / k /N„ Jk γγ Example 5,
114 N γ< ύ^οχ White Solid
o L Step 2
ch3 Y 7i
Y/
F
h3c^ 0 /OH F
kY < o ch3 YY
H II
115 N γ Ύ°' Example 5, White Solid
o h3c ch3 Y , Step 2
Y/ J
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H3C.
0 OH F
ΚΠ 0 CH3
H
SS Ύ Example 5,
116 f'Q' White Solid
0 L .CHo X Step 2
ν ιΊ
ch3
F
h3c% 0 ch3
OH
0 ch3
117 ks 3 I H k.N , a /\/%Z 1) Example 5, White Foam
N γ 0 Step 2
0 ch3
F lT^ ch3
h3c. H3C.
0 OH 0
0 CH3 s
1 H II
118 a 3 N .....A Example 5, Step 2 White Foam
0 ch3
Ι<ίιΊ
ch3
0
H3Cfo 0 ^OH Cl
0 ch3
H II
119 N AN Y^O' f OH Example 5, Step 2 White Foam
0 OH3 Fx
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
120 h3c\ 3 0 F JL /OH xL .CH3 Y γ o ch3 YY< 3 0 ch3 J. ch3 Example 5, Step 2 White Foam
121 H3C\ 0 Cl JL /OH xL /CH3 Y γ o ch3 3 ΑγγγγΑ 0 ch3 xL y^c, ch3 Example 5, Step 2 White Foam
122 h3c^ 0 JL /0H F\ /^ Y^< o ch3 Y^Y II 1 oh 0 CH3 F'xYj Example 5, Step 2 White Foam
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 0 0 I OH Z-CH
S'
rir x 0 ch3
H II
x/N,„ X 0 x^x
N Y 1
123 II 1 0 ch3 X Example 5, Step 2 White Foam
X ( 1 :h
h3c.
0 1 /OH
0 CH3 {/''''S' Xsh3
H II
XX V T '0' /+X
N
124 II 1 0 ch3 S' Example 5, Step 2 White Foam
kx xch3
h3c\ 0 oh
X'' 0 CHo S v
125 - C.N,,/ A xX J Example 5, White Solid
N if 'f 0 CH 3 0 Step 2
XXi
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
.OH Cl
X o ch3 XX
H II
x> X X .n,, A A / Example 5, Step 2
127 N T T° 0 CH3 ΌΗ ΌΙ White Solid
^Cl
Cl
h3® 0 OH Cl
X o CH3 Xx
H II
χχ X ^N„ A Χγ Example 5, Step 2
128 N Π 0 O CH3 ΌΗ T White Solid
γ ^F
Cl
Η=% .OH ®l
' o ch3
H II
X y- XX Example 5,
129 N Ύ r ° sch3 White Solid
o ch3 Step 2
χ\
Ύ Xh3
Cl
Br .OH
fli x O ch3 rAY
H II
A..X x-y
130 N γ Y 0 Example 5, Clear,
0 ch3 Step 2 Colorless Oil
Y/
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c^
0 A OH F
Xl 0 ch3 XiX
H II
131 Sr tf Ox Example 5, Clear,
0 ch3 Step 2 Colorless Oil
jl
X/
F
ΗΆ i OH Cl ,F
Xl 0 ch3 Xif
H II
A· X K
132 'h, / Ό' Example 5, Colorless
0 1 ch3 Step 2 Foam
jl
X/ ^Cl
F
HA 1 OH ch3 ,, F
Xl 0 ch3 XiX
H II
133 Sr Π '0' XX Example 5, Colorless
0 I ch3 Step 2 Foam
jl
X/ ah3
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 3 0
X <0H F
0 ch3 XX
1 H II
k / . X -'Xk Example 5, Step 2 Colorless
135 N T 0 I ch3 O' Tacky SemiSolid
j)
F
η3Α 0 OH ^Cl
aX 0 ch3 ΑΧί
H II
A A k χΝ„ Example 5,
136 N Ό' Xi White Foam
0 ch3 Step 2
Xx ^Cl
Cl
H^o J OH XCI
XX 0 ch3 XX
H II
A k k AD Example 5,
137 N if Oz X White Foam
0 ch3 Step 2
X/
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Appearance
Example
h3cy 0 o^ch3 r°
138 ilX LL Αν yX '0' ch3 I c JH XX yX Example 6B Colorless Semi-Solid
0 ch3 (1 k
A
h3c\ 0 0 γ0Η3
139 ks. Y. N yX '0' ch3 XY yX Example 6A Colorless Oil
0 ch3 χ
X
ch3 I 0
h3cy c 0 ^yCH3
140 XiT A N yX '0' ch3 χγ γΧ Example 6A White Foam
0 ch3 X
X
h3cy 0 0<^ch3 r°
141 XiT Y. N yV Ό' ch3 χχ yX Example 6B White Foam
0 ch3 X
X
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
ch3 I °
0<Y^ch3
h3c^ 0 r°
142 N' I//0' ch3 ) Example 6C White Foam
0 ch3
143 h3c^ 0 X N o^ch3 Λ- ch3 s- λ Example 6A Colorless Oil
0 ch3 V xs
h3c^ 0 0<yCH3 r°
144 V N ch3 S' Example 6B Colorless Oil
0 ch3 V xs
145 H3C\ c 0 JJ· N >^ch3 /0 0 ch3 YyV? o ch3 JL ίι Ί ^X F Example 6A Colorless Oil
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3X 0 0<yCH3 r°
146 ril A JJ N x o' CH3 Xγ Example 6B Colorless Oil
Π 1 o ch3 fjX
F
h3X 0 0<yCH3 r°
147 A . N ¢^,,.J 0 ch3 0 CHs A Xo [Tj^CH3 Example 6B Colorless Oil
h3X 0 o^ch3 r°
148 Χϊ A JJ N A Ό' CHs riT Χ/Αχ Example 6B Colorless Oil
ii I o ch3 ίΓΧF
kJ
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c^ 0 O;yCH3 r°
149 vs. N' c>=\ O Zl ω o X; s ΛΛ GO \ / Example 6B Colorless Oil
150 H3C\ c 0 ί^ιΐ X FN X^ch3 /° F\ /F o ch3 o ch3 Js fi Example 6A Colorless Oil
F
H3C\ 0 o^ch3
152 Y vs. N' o ch3 ΧλΛ o CH3 Js ίΐ Ί Example 6A Colorless Oil
h3c^ 0 O<yCH3 r°
153 vs. N' . /0 o ch3 VAX o ch3 fl Ί Example 6B Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
155 H3C\ O\.CH3 ο γ A 0 ch3 ζ JA, A A. n ]< A o ^A o ch3 A A^ Ak < CH3 Example 6A Colorless Oil
h3c
h3(A 0 V 0<yCH3 A o ch3 H II 1 F
156 N %/ Example 6A Colorless Oil
0 ch3
h3cx 0 0<yCH3 Cl
V A o ch3 H || 1 A^a
157 N AA Example 6A Colorless Oil
0 ch3
cr
h3ca 3 0 O^CHs r°
Av .0 0 ch3 Η II 1 3 rA^ AA < ch3
158 N γ 'Αγ Aj^X Example 6B Colorless Oil
o CH3 +L il
h3<A
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3Y 3 0 0<yCH3 r° F
159 V k> N AA o' ch3 A zA Example 6B Colorless Oil
0 ch3
F' Αγ
h3c\ 3 0 0<yCH3 r° Cl
160 V k> N AA o' ch3 A yA Example 6B Colorless Oil
0 ch3 Zk
cr Az
161 h3cx 0 Y k> N °<yCH3 Aa Y ch3 Q Example 6A Colorless Oil
0 ch3
V
h3Y 0 o^ch3
162 V ks N Aa O' ch3 zAi z^A Example 6A Colorless Oil
0 ch3 Az 0
Ay
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3¥ 0 o^ch3 r°
163 G ¥ ι\Γ ch3 A Example 6B Colorless Oil
0 ch3 v A
h3C¥ 0 0<yCH3 r°
164 ¥ N i/A- ch3 AA AG Example 6B Colorless Oil
0 ch3 ΓΥ°
165 h3C¥ c 0 ¥ JJ- N ><yCH3 /0 0 ch3 YyA o ch3 ll Ί AfBr Example 6A Colorless Oil
GA
Br
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3cy 0 o^ch3 ch3
/0
A o H II ch3 s- $
A A, Ak
166 N Example 6A Colorless Oil
0 ch3 AA
CH 3
h3c\ c 3 0 <yCH3
/0 /CH3
rl· x 0 ch3 A
H II
\ Ji,„ Y. AyA
167 N >< γ o Example 6A Colorless Oil
o ch3
AA
Ay
ch3
ch3
H,C. CY A
0 y ch3
/0 /CH3
Αγ 0 ch3 A^
h 11
168 Y Y N y A A^A>^ Example 6A Colorless Oil
0 ch3
Ay
Ay
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H3y 0 o^ch3 r°
169 kx JN ch3 y^ y. Br Example 6B Colorless Oil
o ch3 yk
Br
170 H3y 3 0 kx s N o^ch3 r° ch3 s- ch3 Example 6B Colorless Oil
0 ch3 Y 's
CH 3
h3c\ 3 0 0<yCH3 r°
171 y^ kx Jk N /0 o ch3 r y1aA V ^ch3 Example 6B Colorless Oil
0 ch3 ίΓ^Ί
yy
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c, 3 O o^ch3 F YF
χθ Y o CH3 YY YA
1 d ii I
173 N Ay,, Yk Example 6A Colorless Oil
o ch3 1
ίΐΊ
YY
h3c\ 0 o^ch3
S. χθ Cl
X o ch3
H II
ks A/N„, y
174 N if 1 ο Example 6A Colorless Oil
0 ch3
f|Y
AY
Cl
o^ch3
H3C\ 3 0 <° F
1 /0 γ o YF
A ch3 YYr
175 ΐ Η II f 1 Example 6B Colorless Oil
ks . χΝΆ _Y\ . AY
N ο γ
0 ch3 1
Η Ί
AA
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c^ 0 ΟγΟΗ3 r°
176 γγ JJ· N γγ ch3 Y^ Y/k/ Cl Example 6B Colorless Oil
o ch3 YY
YY
Cl
°γΟΗ,
178 σ YY°- CH3 YY γΥ/ ^F Example 6B Clear, Colorless Oil
0 ch3 YY
V
F
h3c^o o^ch3 r°
179 k N Ιγ/ ch3 Y ογν F Example 6B Clear, Colorless Oil
o ch3 YY
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
o^ch3
180 c ch3 A^ F Example 6B Clear, Colorless Oil
0 ch3
A
F
h3<¥ 3 0 °γΟΗ3 r° ¥¥
¥ N' . /0 ¥ ° Χ¥·¥ ch3 ¥ ^AA
181 Π 1 o ch3 O y Example 6B White Foam
Al
¥
h3¥ 3 0 ¥ N' ch3 ¥ yy A^A
182 0 ch3 Ai Example 6A Colorless Oil
¥/
Ai
AA
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 0 o^ch3 /°
183 fl X 3 N Qx ch3 f^3 XX F Example 6B White Solid
0
Χχ
F
h3c\ 0 0<yCH3 r°
184 fl X i N < o X ^N„ X „ X< X o ch3 χχ F Example 6B White Solid
o J h3<X
Χχ J
F
h3c\ 0 CX^CHs r°
185 fl X J- N Ία ch3 fX χχ F Example 6B White Solid
o J\ h3c ch3 x^
Xx J
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
0<yCH3
H3C\ .0 ο Y
yL .0 F
YtY o ch3 YY
H II
186 V ^γ N..... Example 6B White Solid
0 L /CH
γ 7|
ch3 Y/
F
H3Cx (X.CH3 ο ^γ
JL /0 F
YY 0 ch3 yy
n V o
187 Example 6A White Solid
0
F
H3C\ (x.ch3 o ^γ
yL .0 F
YYV o ch3 yy
Η II
Y.yV/N,,, A,' Ύυ
188 N ΛΥ Ύ 0 Example 6A White Solid
0 J
h3cY il
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H3Cx o. ,ch3 ο
.0 A
Y Y 0 ch3
H II
γ X\/Y / XX
189 N YY Y 0 Example 6A White Solid
o X
H3c^ 'CH3 X^
F
h3cyo o^ch3
J\.O
0 ch3 pY γ
Γ IT H II
Xz XX
190 N ϊΓ ( 0 Example 6A White Solid
o L ach
1 ch3
F
H3CY°
h3c\ .0
0 Y CH 3
X .0 CL
NY o CH, XX
191 H II Example 6B White Foam
γ,Α Λ, XX
Ν YY Y 0
0 CH,
A Y Yh3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c^ 0 o^ch3 r° h3(\ 0
192 k N ch3 Y^ ί Example 6B White Foam
0 ch3 A 'S
A- ch3
h3c^ 0 0<yCH3 r°
193 kl k J- N G,x ch3 Cl Example 6B Sticky Wax
T Γ 0 o ch3 OH
A^ y
Cl
H3C\ 3 0 0<^ch3 r° F
194 N /0 x 0 ch3 yWJ A kA xCH3 Example 6B White Foam
0 ch3
k
ch3
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3c\ 3 0 o<^ch3 r° ci
Xx XO 0 K JI ch3 Xk /CH3
195 X^ N Y ''k° XaX Example 6B White Foam
0 ch3 X
^ci
ch3
h3A 0 0<yCH3 r°
196 V k N ^TfV 0 ch3 O' Fx ch3AA XX Jk0H Xh ) Example 6B White Foam
aX
197 h3c\ 3 0 XXr k N o^ch3 r° XX°Z ch3 XX ^CH A Example 6B White Foam
o ch3 X
X
( :h
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3<O 3 0 0<yCH3 r°
198 ό N XA o ch3 ch3 X A/\, Xs ΊΓ X Example 6B Sticky Wax
XH3
h3c^ 0 0<yCH3 r°
199 ks. . N ch3 Ό^ c r' Example 6B White Solid
0 ch3
h3c, 0 0<yCH3 r°
201 N 0 ch3 CH3 XX 1 OH XX XI XI Example 6B White Solid
Xi
Cl
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3cy 0 o^ch3 r°
202 ¥ JX N Aa ch3 AA XI F Example 6B White Solid
T i 0 0 ch3 ΌΗ Γ
A
Cl
h3c, 3 0 0<^ch3 r°
203 Gy ¥ N .0 0 ch3 TyVy AA^ AA γι ¥h3 Example 6B White Solid
0 ch3 Ai
Gh3
Cl
204 h3ct h3c 3 ^q3 ¥ ¥ N Y° gA- ch3 ...q rp Example 6A White Solid
0 ch3 A'
A- A
2019201931 20 Mar 2019
Figure AU2019201931A1_D0059
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
209 ch3 i 0 0 h3<x o. J 3 ο /X/° X Ay 0 CH3 X Y y^yj 0 ch3 J. F Example 6A Slightly Cloudy Colorless Oil
210 Ax y k ly, a a IJ nXa o CH3 A F Example 6A Slightly Cloudy Colorless Oil
211 ch3 0<Y^ch3 η3°.ο Xa y X 7< 0 CH3 χ 7< yy> O ch3 J. F Example 6C Clear Colorless Oil
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
ch3
cr
o< V J
h3c 1 ,0
0 ( Colorless
212 y H Nz, 0 ch3 yy F Example 6C Clear Film And Opaque
kx JL A oz Oil
N' τ
0 ch3
|j
y^
F
ch3
h3c\ 3 0 Ox Clear
y 0 0 II ch3 yy F Colorless
213 | H Example 6A Viscous Oil
kx N' ,N„ y o' And Semi-
0 I ch3 Solid
7i
y.
F
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
ΟγΟΗ3
Br r n
All < o cho Αγ
Η II Example 6B Clear
214 k> γ N γ'γγ AA Colorless Oil
0 ch3
Ai
AA
F
h3Y 0 0<yCH3 F
n /A Y
A A o ch3 Yγ
H II
215 k> N' ΫΆ Az Example 6A Pale Yellow Oil
0 ch3
A
A. ^F
F
H3Cx 0 0<^ch3 Cl
O
A A o ch3
H II
216 k> N' A Ά°· Az Example 6A Pale Yellow Oil
0 ch3
A
A^ ^Ai
F
100
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
217 h3a 0 X X N' 0<yCH3 0 ch3 V ch3 Y^ ch3 Xv XF Example 6A Pale Yellow Oil
x^ ^ch3
F
h3a 0 o^ch3 r° f
218 X X N' Ό ch3 'Xa ,f Example 6B Pale Yellow Oil
0 ch3 Y^ jj
Xx
F
h3a 0 0<yCH3 r° Cl
219 N' A ch3 Xv 'AA ^f Example 6B Pale Yellow Oil
0 ch3 Y^ s
X/ 'Xl
F
101
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
h3Y 0 0<yCH3 r° ch3
220 Hl Y J N Qa ch3 y AA Example 6B Pale Yellow Oil
0 ch3 yA s
Αχ Ah3
F
h3y 0 0<yCH3 r°
221 Αη Y J- N Qa Ox ch3 iAci Example 6B White Foam
0 ch3 A
A 'xi
Cl
h3y 0 0<^ch3 r°
222 aA Y J- N Y '0' ch3 y Example 6B White Foam
Π 1 o ch3 yA
Ax x
Cl
102
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
H3C\ CK /CH3 J ο ^γ
/ci
Yy ° ch3 YY
H II
k Y/N„, A YY
223 N Ύ Ό Ai Example 6A White Foam
0 ch3
Υ
Yx ^Cl
Cl
H3C\ Ox.CH3 ο ^γ
/Cl
Y^Y o CH3 γγ
Y/N, Y YY
224 Ν Ύ Ό' A Example 6A White Foam
0 ch3
τ
Cl
ΟγΟΗ3
H3CA /0 0 <
/X /0 F
KT o H II ch3 YY Slightly
225 Υ,ΥΥχΥ YY Example 6B Opaque
0 Colorless Oil
0 ch3
Y/
F
103
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
F
H3C^°fo^ h3cA Π 0 ch3 All F Example 1;
226 Y A '0' A^ T Example 2D, Steps 12; White Semi-
ch3 0 CH 3 Example Solid
|j 3A;
F' A^ Example 4A
F
F F
0 ch3
H2N„ A \ _ X A^ k__
227 [ 0 F Example 5, White Glass
ch3 Step 1
r
As „ JA
Fz F F
H3C.
0 F
/OH F
Yy 0 ch3 rA
H II
228 /N N ]< Ύ A '0' T Example 5, Colorless
0 1 CH 3 Step 2 Foam
|1
A^. Jl
F' F F
H3Cx 0. /CH3 ο F
/0 F
AYY 0 ch3 Ail
H II
A A /N A As. Y Clear, Colorless Oil
229 N ]< Y Ό T Example 6A
0 Ch 3
jl
II
F' F F
104
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
°Y M'O ch3 F
230 X® H N ' 0 Ά- ch3 XF XAf Example 6B Clear, Colorless Oil
0 ch3 Y
F' Λγ
F
0 ch3 X F
232 h2n^A ch3 Y Example 5, Step 1 White SemiSolid
Y
F
233 ch3 0 ch3 h3cl 1 H II I h3c^Y n Ax 0 CH3 X γ Example 1; Example 2A; Example 3A; Example 4A Clear, Colorless Viscous Oil
F
234 h3c o n„ HsC^I Π ch3 o o Y CH3H3Cv H?C. Cn3 yx -YX Example 1; Example 2A; Example 3 A; Example 4A. Clear, Colorless Oil
%
F
105
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
235 0 ch3 ch3 0 ch3 J ch3 T/CH3 Xt CH, XJ Example 1; Example 2A; Example 3 A; Example 4A. Clear, Colorless Oil
X
h3c/ Xh3 :h3
236 0 ch3 ch3 0 ch3 J ch3 ΧΧ\η3 Example 1; Example 2A; Example 3 A; Example 4A. Clear, Colorless Oil
X
H3CT Xh3
237 ch3 O CH3 Y' ‘YY'A-W ch3 o ch3 A. y^cHs ch3 Example 1; Example 2A; Example 3 A; Example 4A. Clear, Colorless Oil
106
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
238 0 A ch3 z/\ ^F Example 1; Slightly
ηηΧ°ΎΚ 1 x^ Example 2A; Example 3A; Example 4A. Cloudy Colorless Viscous Oil
ch3 0 ch3 Xz
F
239 ch3 /F Example 1; Slightly
H H3C. /O. /N o 11 iT Example 2A; Cloudy
X u Example 3A; Colorless
hcY ¥ X° Example 4A. Viscous Oil
ch3 o ch3 F
240 ch3 Example 1; White Foam
1 o F Example 2A;
0 ch3 ¥ XX Example 3A;
H3Cv°v^ h3c¥T il A Example 4A.
ch3 0 CH3 /Ox h3X x YA
XX
F
241 o CFU Example 3H Colorless Oil
h3c^I Ii A'x ¥h3 Steps 1-2; Example 4A.
ch3 0 ch3 V
107
2019201931 20 Mar 2019
Figure AU2019201931A1_D0060
108
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
245 ch3 Example 1; White Foam
1 o Cl Example 3C;
0 ch3 A A Example 4A.
η3ο^Ί Π A-
ch3 0 CHH33C/O' Αγ
Cl
246 h3c. Example 1; White Foam
1 Example 2A;
Ck F Example 3A;
0 ch3 t+A Example 4A.
h3c'n Π ” A L^X
ch3 0 CH3 .0.
r ch3 Ai
L+x
F
247 h3c. Example 1; White Foam
1 Example 3C;
ex Cl Example 4A.
o ch3 A AA
η3ο^Ί Π A L^x
ch3 o
ch3^c\ ch3 Aii
k/
Cl
109
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
248 H3C. Example 1; White Foam
1 Example 2A;
0 ,ch3 Example 3A;
0 ch3 \Yy Example 4A.
ΦΫΑ CH3 0 CH^CX ch3 AyA
ax A
A,
ch3
249 o Example 3G, Steps 1 and White Foam
o ch3 H II 1 Yh3 2; Example
¥ΎβΜ Αύ 4A
ch3 o ch3 Y Y
A Y
cr Yh3
250 F Example 1; White
Example 2A; Semisolid
o ch3 Ail Example 3 A;
AA /CH3 Example 4A.
ch3 0 ch3 A
AA ACH3
0
251 H3Y Example 1; White
u Example 2A; Semisolid
0 ch3 Η II 1 s's' K. Example 3 A;
Y Example 4A.
^°ϊν¥ AA /CH3
ch3 o ch3 Ail
h3c J AA ACH3
0 0
110
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
252 ch3 Example 1; White
Example 2A; Semisolid
H3C 0 N„ h3cYT Π 0 ch3 Yp Example 3 A;
Y o' -X ,o/H3 Example 4A.
CH3 0 ch3 xY-
A_/CH 3
h3c- 0
253 H 0 II ch3 Γϊ -CH3 Example 1; Example 2A; Clear, Colorless Oil
H3C 0 N„ h3cYT Π Y o' AA- ,o/H3 Example 3 A; Example 4A.
CH3 0 ch3 xY-
Ax A /CH 0 3
CH 3
254 0 II ch3 Οχ Example 1; Clear,
H if uh3 Example 2A; Colorless Oil
H3C 0 N„ η3ο^Ί Π Y o' AA 'F Example 3 A; Example 4A.
ch3 0 ch3 xY-
A^
ox ch3
255 H 0 II ch3 Γϊ Οχ ch3 Example 1; Example 2A; Clear, Colorless Oil
H3C 0 N„ h3c^I Π Y o' AY 'ch3 Example 3 A; Example 4A.
ch3 0 ch3 xY-
Ax Ah3
Οχ ch3
111
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
256 ch3 Example 1; Clear,
1 0. Example 2A; Colorless Oil
0 CH3 ¥ ¥ Example 3 A;
“υΥ'Ά kcHa Example 4A.
ch3 0 ch3 ,o, A Til
k ¥H3
257 0 H II H3C, A ¥ Example 1; Clear,
H Example 2A; Colorless Oil
υυΆ kCH’ Example 3 A; Example 4A.
ch3 0 ch3h3c. Aii
kA k /CH3
258 Example 31, White Foam
υΐΊβ 0 Example 4A
D
0 ch3 k¥
H II
h3c O N,„ A HkC'J il 1 ¥A
CH3 O CH3 -O, / 3 h3c¥ A
/A
0
I ch3
259 Example 1; White Foam
0 H || ch3 1 Example 2A;
H3C, -0, ,N„ X \A\ Example 3 A;
h3c¥ ¥ 1 1^ F Example 4A.
CPU 0 CPU
h3czV Ί ch3
A
F r
F
112
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
260 0 Η II H?c\ CH3 yy Example 1; Example 2A; Colorless Oil
H3C. .0. .N„ x yy Example 3 A;
H,cYY i 0 ch3 Example 4A.
CH3 0 CH3H3C. yy
YH3
261 0 H II H?c\ CH3 yy< ,ch3 Example 1; Example 2A; Colorless Oil
H3C. .0. .N,„ x yy Example 3 A;
«Λ Y r° Example 4A.
CH3 0 CH3H3C. yy
CH,
262 0 H II H?C. CH3 yy Example 1; Example 2A; Colorless Oil
HAT .0. . N/, X yy Example 3 A;
«γ y y 0 τ έ Example 4A.
ch3 0 ch3h3c X
y^
263 F\ 0 ch3 Yy Y Η II 1 Example 1; Example 2A; Colorless Oil
yYX y^0 zCH3 Example 3 A; Example 4A.
ch3 0 ch3 k Yy
AY
O
113
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
264 ch3 o ch3 A η-Α ch3 0 CH3 ch3 Example 1; Example 2A; Example 3 A; Example 4A. White Foam
265 CH3 F 0 C/XVt ίΑΛΑ CHs 0 ΗΗ3^°η^ fXf F Example 1; Example 2A; Example 3 A; Example 4A. Colorless Oil
266 H3C-o ch3 I H3C. I .CH3 < .F τ η n mf 0 Y N Vo ΛΑΕ o CH3 .ch3 X JJ 0 F Example 1; Example 2A; Example 3A; Example 4A. Sticky Wax
114
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
267 H3C^X CH3 | H3CT YCH3 < F YH s rΓΪ 0YnX°XA Ch3 ° έΗ= YfX F Example 1; Example 2A; Example 3A; Example 4A. Sticky Wax.
268 oCH= h3c. o ch3 Y YAY CH3 0 CH3H3C^zY 1 ch3 Example 31, Example 4A Oil
269 ch3 ch3 0. o ch3 y Y YAY ch3 0 ch3 H3C Yp |1 η3ο^ϊϊΧ Example 31, Example 4A Oil
115
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
270 ch3 Example 1; Colorless Oil
1 O Example 2A;
o ch3 0Y Example 3 A;
H3Cv°v^ h3cyT il Ή 00 Example 4A
ch3 o ch3 /O. h3c Ί ch3
ch3
271 /Y/Y Example 1; Colorless Oil
H 0 II ch3 v il Example 2A;
H3C. .0. .N ,, Y\ Y 00 Example 3 A;
V Y r o Example 4A
ch3 0 CH3tY°^ Ί SCH3
0/
CH 3
272 ch3 Example 1; Example 2A; Colorless Oil
0 ch3 00 Example 3 A;
η3ο^Ί Π 00 Y00 Example 4A
ch3 0 ch3 /0 h3c Y V Y CH3
0 0h3
273 H o ch3 γ YY Example 1; Example 2A; Colorless Oil
h3c o n„ η3ο^Ί Π -γγ Example 3 A; Example 4A
ch3 o CH3 ί
J
o
ch3 F
116
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
274 ch3 Example 1; Colorless Oil
1 H,C O Example 2A;
o Example 3 A;
H3C o n„ HsC^I ΪΙ A· Κ/Χ/ Example 4A
ch3 o CH3H3Cx
Οχ
ch3
275 o CHq XX Example 3F; Colorless Oil
H II Example 4A
η3ο^Ί Π ολχ
ch3 0 ch3 / h3c x
U
F
276 Example 3F; Colorless Oil
Η 0 II Ϊ 3 \ H Example 4A
Η3°ν°νΝ h3cXT π Ά Λ./ V
ch3 0 ch3 |A| °^CH3
XX
277 X Example 3F; Colorless Oil
H 0 II I 3 \ H Example 4A
H3Cv°vn H3cXT if Ά Λ./ V
ch3 0 ch3 XX CHs
XX
117
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
278 0 CHq AA Example 3F; Colorless Oil
H II Example 4A
“ύΥ'Λ·
ch3 0 CH3 X- h3c¥ yG ¥
x
F
279 o CFU Example 3F; Colorless Oil
H II Example 4A
StyA •AG
ch3 o ch3h3ct yG
G. y
F
280 Example 3F; Colorless Oil
0 ch3 Η II 1 GT Example 4A
GYG A”' T
ch3 0 ch3 ΙΊ ch3
ch3
281 zto\/F Example 3F; Colorless Oil
0 ch3 Η II 1 GT Example 4A
GYG A”' T
ch3 0 ch3 ΙΊ ch3
ch3
118
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
282 x^/CH3 Example 3F; Colorless Oil
H 0 II I 3 \ H Example 4A
H3C 0 N„ H3C^A Π A
CH3 0 CH3 -0. h3V An
Ay
F
283 Example 3F; Colorless Oil
H 0 II I 3 \ H Example 4A
H3C 0 N„ η3ο^Ί if A° yxAA
ch3 0 ch3h3c^ An
Ay
F
284 Example 3F; Colorless Oil
H 0 Ϊ 3 \ H Example 4A
ΑΎΝΆ 1'
ch3 0 ch3 i|k Ah3
AA
F
285 /F Example 3F; Colorless Oil
H 0 A3 \ H Example 4A
ΑΎΝΑ
ch3 0 ch3 Ay ch3
yA
F
119
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
286 Example 3F; Colorless Oil
0 Η II Ϊ 3 \ H Example 4A
XYX
ch3 0 ch3 Af °'ch3
\y
f
287 Example 3F; Colorless Oil
0 Η II Ϊ 3 \ H Example 4A
ΥΎΧ
ch3 0 ch3 XYaCH3
X
F
288 /F Example 3F; White Foam
( H3Cx pyx- Example 4A
ch3 0 ch3 .o, H3V Xy CHs
kJ
F
289 Example 3F; Yellow Sticky
( Η3χ Example 4A Wax
ch3 0 ch3 .ox H3V XF
F
120
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
290 Example 3F; White Foam
( h3c^ pyy- ch3 Example 4A
ch3 0 CH3H3C/ Y CH3
X
F
291 pyy- ch3 /Y/F Example 3F; Yellow Sticky
( h3c^ -/ Example 4A Wax
CH3 0 CH3H3C, Y^ F
X
F
292 0 CPU Example 1; Colorless Oil
H II Example 2A;
X Yr0' azy y F Example 3 A; Example 4A
CH3 0 CH, ,OX H3fc Y^ Y CH3
F'
293 F Example 1; Example 2A; Colorless Oil
0 ch3 Xjl Example 3 A;
xyX yXa Example 4A
ch3 0 ch3 ,0. H3cY ^Y \ Y X ch3
y F
121
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
294 ch3 Example 1; Example 2A; Colorless Oil
0 CH3 All Example 3 A;
H3C 0 N,„ A H3c^[ Π f xo Example 4A
ch3 0 ch3 An
L II
ch3
295 o CH-, Ατι Example 3F; Colorless Oil
H II i 1 II Example 4A
H3C 0 N,„ X TI 1 0A\,AA
CH3 0 ch3 Fyk
AA
ch3
296 Example 3F; Colorless Oil
0 Η II ch3 An Example 4A
Xr.....Λ
ch3 0 ch3 f VA
AA
ch3
297 Example 3F; Colorless Oil
0 Ϊ 3 \ N Example 4A
Xy'Z
ch3 0 ch3 Ail
AA
ch3
122
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
298 ch3 F Example 3F; Example 4A Colorless Oil
0 CH3
H II 1
h3c 0 N,„ A η3ο^Ί il 1 AT
ch3 0 ch3 [Γί
\A
299 ch3 F Example 3F; Example 4A Colorless Oil
0 ch3 rV
H II I
h3c 0 N,„ A h3c^J il 1 o'
CH3 0 CH, H3C' A
\_A
F
300 o Η II CH3 XX A Example 3F; Example 4A Colorless Oil
h3c o n,„ A h3cXT 11 1 cT Α·Μ
ch3 o ch3 Fx CH3
ch3
301 o Η || ch3 Yr zF Example 3F; Example 4A Colorless Oil
H3C O N,„ A HsC^J ΪΪ 1 cT 1'
ch3 o ch3 Fx Til F
ch3
123
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
302 a\7h3 Example 3F; Colorless Oil
0 Η II Ϊ 3 \ H Example 4A
“ΖϊΥ
ch3 0 ch3 XX
303 o CH-, Example 3F; Colorless Oil
H II ! 1 II Example 4A
H3C O N,„ A H3cXf Π 1 oA-V
ch3 0 ch3 Xil
ch3
304 Example 3F; Colorless Oil
o CHs X V Example 4A
;yy.....Y Λ.·Μ
ch3 o ch3 Χη
^Υ
ch3
305 o CHi Xti Example 3F; Colorless Oil
H II ! 1 II Example 4A
h3c^1 Π 1 AxV
ch3 0 ch3 X|1
kJ
F
124
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
306 /CH3 Example 3F; Colorless Oil
H 0 II ch3 O' Ύ Example 4A
H3C 0 N,„ Λ ox Y YY
CH3 0 ch3 yY
YY
F
307 H 0 II CH3 Y f Example 3F; Example 4A Colorless Oil
H3C 0 N„ η3οΊ Π / θ' J
ch3 0 ch3 Y f
YY
308 H o II ch3 Y f Example 3F; Example 4A Thick Oil
H3C o n„ η3οΊ Π / o' T J
ch3 o ch3 rnF
YY
ch3
309 H 0 II ch3 Y f Example 3F; Example 4A Colorless Oil
H3C 0 N„ H3cX Π / o' z\· T
ch3 0 ch3 Y f
YY
F
125
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
310 0 ch3 ch3 Ach3 XXA^CH3 Example 5, Step 1. White Powder
II 1 h2Nz„J\oA.
I ch3 A
X
h3<X c \h, :h3 3
311 0 ch3 ch3 Example 5, Step 1. White Powder
II 1 H2N'- ΛΑ
1 ch3 A
X
h3ct TH3
312 ch3 /CH3 o ch3 A ¥¥ Example 5, Step 1. Clear, Colorless Thick Oil
h2n,„. ΑχθΑ
ch3 zk
h3c^V
ch3
126
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
313 o ch3 γ^ AY CH3H3C^A F Example 5, Step 1. White Powder
314 F 0 CH3 Y Y hY>/YY CH3 -A F Example 5 Step 1. White SemiSolid
315 0 CH3 Υ V CH3 -A F Example 5 Step 1. White SemiSolid
316 ch3 1 o ch3 γ^ AY h4<-YoAJY CH3 n -- γ F Example 5, Step 1. Clear Glass
127
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
317 0 H2nYL, ch3 AAt AA 'V Example 1; Example 2A; Example 3A; Example 4A, Example 5, step 1. Pale Purple Sticky Wax
1 F jl
A^
F
318 0 ch3 £-( V o / A^ Ach3 Example 5 Step 1. Colorless Oil
A J
319 0 I I ch3 yaa Example 5, Step 1 White Foam
yA
ch3 A k
A
1 l· 1
320 0 h2n„,^Xo. ch3 Fx <AA yA YF F Example 5, Step 1 White Foam
ch3 A
A
F — — F
128
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
321 0 ch3 A 0 /oAh3 Example 5, Step 1 White Solid
II i Η2ΝΆοΛΎ «s, -X
ch3 k A
ch3
322 0 ch3 Example 5, Step 1. Colorless Oil
ch3 X
323 0 H2nA-o- c c ch3 l+ycl Example 5, Step 1. Yellow Oil
0H3 q η3Α ' r
Cl
129
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
324 h3c Example 5, Yellow Oil
Ί Step 1.
Οχ F
0 ch3
ΥΥγ CH3^O^A ch3 A A^
F
325 h3c. Example 5, Yellow Oil
Ί Step 1.
Οχ Cl
o ch3
CHs^O^A CH3 A^
Cl
326 H3C Example 5, Yellow Oil
Ί Step 1.
Οχ /CHs
o ch3 η YYr
έγ°Α\ CH3 kA
ch3
130
2019201931 20 Mar 2019 *
Figure AU2019201931A1_D0061
Prepared
According .
Τθ Appearance
Example
Example 5, White Foam Step 1
Example 5, Step 1
Example 5, Step 1
Example 5, Step 1
White Foam
White Foam
White Foam
131
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
331 F Example 5, White Foam
Step 1
0 I I ch3
H2N„, A. XaX
[ ch3 h3cA A \ ch3
Af
332 F Example 5, Clear,
Step 1. Colorless Oil
0 I I ch3 aX
A XqZ. XkCH=
ch3 Xil
F' XX
333 H3A Example 5, Light Brown
u Step 1. Oil
0 I I ch3 aX
H2Nz„ XVCH=
ch3 Xil
H3C-o- XX
334 ch3 Example 5, Pale Yellow
Step 1. Oil
0 I I ch3 aX
H2N,„ XVCH=
ch3 aX
Η3Α XX o^CH=
132
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
335 ch3 Example 5, Pale Yellow
Step 1. Oil
0 I I ch3 Ail
H2N,„ G '0' G^G . /CH3
T 0
ch3 s
G^ A/CH 3
h3c 0
336 0 II ch3 ch3 Example 5, White
c il Step 1. Powdery
h2n„, JX o' G^G . /CH3 Solid
0
ch3 s
Gy G /CH 0 3
CH 3
337 Example 5, Clear,
0 || ch3 v il ch3 Step 1. Colorless Oil
H2N,„ a θ' GyG F
ch3 Y^
Gy
Οχ ch3
338 O. Example 5, White
0 || ch3 y il ch3 Step 1. Powdery
H2N,„ JX G^G Solid
O' ch3
ch3 Y^
Gy xh3
ch3
133
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
339 0 I I ch3 Οχ ch3 Ak Example 5, Step 1. Clear, Colorless Oil
(T
CH3 0 h3c¥ r k
k kCH 3
340 0 I I ch3 f .F Example 5, Step 1. White Solid
h2n,A Ό Ay
ch3 h3¥ ¥ A |1
F^ r
F
341 0 ηζνΆ° h3c, ch?3 AA AA kH3 Example 5, Step 1. Thick Oil
ch3h3c kA 'S
A- ^ch3
342 0 H2N„, Ak0 H?C. 0¾ AA AA /CH3 Example 5, Step 1. White Solid
f ch3h3c
kx
ch3
134
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
343 0 h3c ch3 -X/ ^F Example 5, Step 1. White Solid
ch3h3c yY X
F
344 F, 0 ch3 Η2ΝΛοΧ XX yA O.CHa Example 5, Step 1. White Solid
CH3 F, X
y \ /CH 0 3
345 0 I I ch3 =, Χγ CH3 1 A° Example 5, Step 1. White Solid
Xo' xx
1 ch3 fx
0. ch3
346 0 CH 1 ox chY 3 x\ F JAF '''f Example 5, Step 1. Thick Oil
H2N„yo. χχ
CH3 o h3cA r A
A a
X F F
135
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
347 HsCy Example 5, Step 1. White Solid
O HznY, chX yyf Ay
ch3 aX
aX
F
348 h3c' 0 h!X- ch3 YAYY X/Y/ Example 5, Step 1. White Solid
ch3 'xX/Xh3
aX
F
349 /CH3 ch3 0 1 3 1 Example 5, Step 1 Oil
0 I I 0. ch3 XX
h2n„, A
ch3 h3c' '°X A
oX
I ch3
136
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
350 0 ch3 h2Nq.^L0A\ Example 5, Step 1 Oil
ch3h3c^J· y CH3
o-k X
I ch3
351 o I I ch3 ch3 °\x^A ch3 yy Example 5, Step 1 Oil
H2N,,.y y^Ay
An
h3cx Ay
352 H3% χΑ X o ch3 y Example 5, Step 1 Colorless Oil
h2Nx„ Jky
Γ ch3 y
yA
F
137
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
353 ch3 Example 5, Colorless Oil
1 /° Step 1
0 11 ch3 <
h2n„ Λ ^y
ch3
yy
/O H3C
354 0 II ch3 X- f Example 5, Step 1 Colorless Oil
h2n x Ύ
ch3 XX 1 <k ch3
yy
355 0 II ch3 X- f Example 5, Step 1 Colorless Oil
h2n X V
1 ch3 XX 1 CH 3
yy
356 0 II ch3 X Example 5, Colorless Oil
Step 1
h2n Ύ χΛ- A
1 ch3 Xk f ch3
y^
F
138
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
357 s p CH3 X-CH3 XX F Example 5, Step 1 Colorless Oil
358 O CH3 F Η2Ν.ΧοΧ|'Γ< ch3 < X Xh3 XX ch3 Example 5, Step 1 Colorless Oil
359 o ch3 F Η2Ν..ΧοΧ'Γ< ch3 ch3 XX ch3 Example 5, Step 1 Colorless Oil
360 o ch3 xXX h2N/,,.^Xo/L CH3 CH3 χΧ F Example 5, Step 1 Colorless Oil
139
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
361 Example 5, Colorless
0 II ch3 At Step 1 Foam
h2Nz„ A Ό' Λ Y Y
Γ ch3 rAA 1 ch3
00
F
362 A Example 5, Colorless
0 || ch3 At Step 1 Foam
h2Nz„ A O' Λ Y y
ch3 YY ch3
00
F
363 0 II ch3 AfF Example 5, Step 1 Colorless Oil
h2Nz„ A o' 0Y YY
ch3 YY /OYh3
00
F
364 0 II ch3 AfF Example 5, Step 1 Colorless Oil
h2Nz„ A o' 0Y YY
ch3 YY AH3
00
F
140
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
365 0 h2Nx,,^A0/ ch3 ch3 A Y Az xh3 Example 5, Step 1 White Foam
h3Y A^x
366 0 H2nJ10 ch3 z r' Example 5, Step 1. Sticky Wax
ch3 /0 h3c Ύ Ax 1 CH 3
F
367 o Yo ch3 z r' Example 5, Step 1. Sticky Wax
ch3 .o h3V Ύ Ax 1 F
F
368 o Yo ch3 z f Example 5, Step 1. Sticky Wax
ch3h3c Y Ax 1 Ί ° ch3
F
141
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
369 o ch3 XXXF H2NxAA/U CH3H3C^k F ax F Example 5, Step 1. Sticky Wax
370 S P ΡΊ h2n,, XoA CH3 Pa ch3 Example 5, Step 1 White Foam
371 0 CH3 /VF hX<AX CH3 FX\ Pa ch3 Example 5, Step 1 White Foam
372 /CH3 0 CH3 X |X h2n,, Ao A ...-Ύ CH3 A Pa ch3 Example 5, Step 1 White Foam
142
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
373 0 II CH3 ATf Example 5, Step 1 White Foam
H2N,, ¥ '0' Ax'AT
I ch3 Fx 1 I CH3
ch3
374 0 II ch3 AA ¥ Example 5, Step 1 White Foam
H2N,, J-k '0' X.-XA
Γ ch3 Fx I 1 Til F
AT
ch3
375 ch3 Example 5, Colorless Oil
X F Step 1
0 I I ch3 a A X 1
Η2Ν/„. X '0' y,X
Γ ch3 A
AT
376 ch3 Example 5, Colorless Oil
X F Step 1
0 I I CH3 A if X 1
H2N/„ X '0' Y..-M
I CH3 x h3c .0.
AT
F
143
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
377 0 II ch3 k;?YCH3 Example 5, Step 1. Thick Oil
1 ch3 AA
378 0 h2n,„^X iHs All 0Α..·Ά Example 5, Step 1. Thick Oil
ch3 A|i
L+k
ch3
379 0 II ch3 Example 5, Step 1. White Solid
h2Nx,, Λο AaU
ch3 kil
ch3
380 0 h2n, CH3 Cfl Example 5, Step 1. Thick Oil
ch3 AA
F
144
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
381 0 II ch3 Π /CH3 Example 5, Step 1. Thick Oil
H2N„, A..·'''
ch3 fl
F
382 0 II ch3 X f Example 5, Step 1. White Foam
H2N„, Λ 0 s A
Γ ch3 f^ 1 F
X^z
383 0 II ch3 Γ rF Example 5, Step 1. White Solid
h2n„, Λ 0 A^
Γ ch3 A 1 F
Xxz
CF 3
384 0 II ch3 Γ rF Example 5, Step 1. White Foam
H2N,„ Λ 0 A^
Γ ch3 A 1 F
X^z
F
145
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
385 Λ Example 5, White Foam
0 II ch3 r Step 1.
h2n Y y^·' Yy J
ch3 1 F
rY
X,
F
386 H3C^ Example 5 Matte White
O ZOH F Step 2. Solid And Clear Oil
Yy O ch3 YY
H II
\ Yk X xky. Y
N 1 °
O ch3
I]
F
387 H3Ck Example 5 Matte White
0 ΧΟΗ F Step 2. Solid And Clear Oil
0 ch3 yy
N H Λ kJ
0 ch3 F
146
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
388 Example 5, Step 2. Clear, Colorless Oil
Y X N .OH Nz„ X Υ x. A
0 CH 3H3C^ yA ch3
yY
F
389 H=c'o ό XOH V 0 A ch3 '°^A y ch3 AH Y^ch3 Example 5, Step 2. Colorless Foam
0 ch3 A A
A IJ
H3cY ( XCH3 :h3 3
390 ό XOH Y 0 A ch3 cA y γΑ- ch3 YHh3 Example 5, Step 2. Colorless Foam
0 ch3 Y
A
h3A ΌΗ3
147
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
391 H3Csn ch3 Example 5, Clear,
0 Step 2. Colorless Oil
Ah XOH 0 ch3 Ύν xCH3
H II
X / aX
N V τ 0
O CH,
Ail
AA Xh3
ch3
392 A. Example 5, Semi Solid
O .OH F Step 2.
ch3 aa
Vs. N A A^
U 1 1
F ί
F
393 h3c CH 1 Example 5, White Foam
0 3 Step 2.
°H Ck F
0 ch3 XA
vs. , N X·
0 AX'
Ax
F
148
2019201931 20 Mar 2019
Figure AU2019201931A1_D0062
149
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
397 H3® Example 5, White Foam
0 .OH z. VF Step 2
χΧ T o H II ch3 χχΧ F
X Z- ΚαΛ X YY
N Π 1 0
0 ch3
Y
Y
Γ Γ
F
398 H3% 0 Example 5, White Foam
XOH 0 ch3 Step 2
χ X AY xch3
h II I
X A xX
N Y 1 0 I
o ch3 A
X 'll
X
OF ''o'' Xh3
399 h3cx Example 5, White Foam
o ch3 1 3 Step 2.
.OH o. /Cl
CH 3 γ χχ
X i\T γΑ YyY
o ch3 .o
h3c X
Y, A
Cl
150
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
400 YY h3c. Example 5, White Foam
0 1 Step 2.
.OH Οχ F
O CH3
Y / N ί
0 ch3^o. A s
ch3 A/
F
401 HA H 3Y Example 5, White Foam
O Ί Step 2.
.OH Ox /Cl
Ai ch3 A^
Y J N O -κΑο' ch3 .ov r ch3 A^x
kyx
Cl
402 ΎΥ h3Y Example 5, White Foam
0 /OH 1 Οχ /CH3 Step 2.
An ch3 η
Y JL N yA
O ch3^ox Ail
ch3 kA
ch3
151
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Appearance
Example
403 HsCa h3 ca Example 5, Step 2 Colorless Oil
A s N OH H Aa O 7 CH; A^ χΑ>
o ch3 Y A
χ
| ch3 F
404 A A J- N XOH χΑ 0 A H3C. crf3 O' A ch3 Example 5, Step 2 Colorless Oil
O CH3H3C χΧ
Χγ
/O h3c
405 I ch3 1 3 Example 5, Step 2 White Foam
ό χΟΗ X 0 7 ch3 ο^γ x /X o
0 CH3 / h3c r Y ° ch3
X Y
0 Ah3
152
2019201931 20 Mar 2019 *Cmpd.
No.
406
H,C.
407
408
Structure
Prepared
According
To
Example
Appearance
Figure AU2019201931A1_D0063
CH,
Example 5, Step 2
White Foam
H,C
Figure AU2019201931A1_D0064
Example 5, Step 2
White Foam
H,C
Figure AU2019201931A1_D0065
Example 5, Step 2
White Foam
153
2019201931 20 Mar 2019 *Cmpd.
No.
409
410
411
Structure
Prepared
According
To
Example
Appearance
Figure AU2019201931A1_D0066
Figure AU2019201931A1_D0067
CH,
Figure AU2019201931A1_D0068
Example 5, Step 2
Example 5, Step 2
Example 5, Step 2
White Foam
White Foam
White Foam
154
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
412 _/CH3 /CH3 Example 5, Oil
o 0 Step 2
Ay .OH H3C, 0 CH3 > AX
H II |
x a. ,Χ,Λ A> χΥ
N ¥ i i
O ch3h3cXxY,
/J/
0 I
ch3
413 h3cx Example 5, White Foam
o CH I 3 ΐ Step 2.
.OH O, /X /F
XX ' o ch3 r iY
H II f
\Χ,Λ xy
N ¥ i ° i
O CH3 .O, X
h3 3a jl
ii
f
F
414 h3c ch3 Example 5, Thick Oil
0 i .OH Step 2.
y o ch3 nA
H II 1
-X/XYk /X ΑχΧ
N Π [ 0 1
0 ch3h3cXxA \ ch3
X ΤΗ,
155
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
415 H3A Example 5, White Foam
0 I Step 2.
Ay XOH 0 CH AaCH3
H II 3 ii
k X .N /,, k\ X
N γ 1 0
0 ch3h3c \X ch3
XX
ch3
416 h3c Example 5, White Foam
0 I F Step 2.
X .OH
γ 0 ch3 Xk
I H II
k A-. A, A XX
N 1 r 0
0 CH3H3Cx - ch3
X^
417 H’c'o I Example 5, White Foam
,OH F. Step 2.
rV O CHq
H II
k X N„ ,x Χγ X /CH3
N y 1 ° o
o ch3
V ||
X II /h3
156
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
418 Hsk Example 5, White Foam
O ch3 1 3 Step 2.
OH R 0
O ch3 χΧ
H II
ks J· XN ,,, yk
N r
o ch3 k y
Υ
y
o \ _ . .
ui-i3
419 H3C. Example 5, White Foam
0 CH3 1 3 FX F Step 2.
oh 0
H 0 II ch3 χΧ j F
k 3 k.N ,,, yk Χχ
N γ o^X
0 ch3 n >
η3ο' Γ Υ
A y
F — —F
F
420 AX Example 5, Colorless
(J I Γ Step 2. Foam
k .OH
Xil / o ch3 YX
H II
k k ^k /CH3
N T f ° O
O ch3
Ϊ1
y \ Χ 3
F 0
157
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
421 k. H3C, Example 5, Clear,
A OH u Step 2. Colorless Oil
A H 0 II ch3 Aii
k F k/ N„ A D' AAAych3
N T 0 [ ch3
kA
h3c^_ AA k /CH3
o 0
422 h3c. ch3 Example 5, Clear,
0 1 OH Step 2. Colorless Oil
Π H 0 II ch3 Ail
k γ k / N„ , A AA^ /Ch3
N ¥ 0 I ch3 o' YY
Ai
AA A /CH3
H 3C' 0
423 h3c. Example 5, Colorless
0 Step 2. Foam
A OH H 0 II ch3 Y^^CH3 Γ ¥
k γ N„ A ¥ AyA/CH3
N 0 1 ch3 yy
Ail
AA AHa
ch3
158
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
424 Example 5, Colorless
.OH Ck Step 2. Foam
Ai r o ch3 Ay ch3
H II
¥ J- GGY
N Y 1 o ch3 Ό' F
G
G
Ox. ch3
425 YC Example 5, Clear,
0 .OH -Οχ Step 2. Colorless Oil
Aii Γ o ch3 agy ch3
H II
¥ Y Y G yG
N T T 0 ch3 Ό' G yh3
G όη3
0. ch3
426 H3¥ Example 5, Clear,
0 un 1 3 Step 2. Colorless Oil
.OH O.
Aii Γ o ch3 AG
H II
¥ A γ N/-r 'Q>' yG .AN
N 0
0 ch3 Xx
h3c' r A il
A G./CH3
o
159
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
427 nAH3 Example 5, Clear,
0 .OH 0 Step 2. Colorless Oil
T 0 ch3 fir
H II
A „ A/kX Aa
N Π I 0
0 CH3H3C X . ch3
Jt/CH3
428 H3A AA Example 5, White Foam
O -OH 0 Step 2.
Xv O ch3^ r
A A. N XX
0 ch3 ζγίΗ;
X^
F
429 H3C h3cX X Example 5, Sticky Wax
0 Step 2.
-OH Λ
AX O chX
A Jk N ch3
0 ch3 αχ X1
γΑ 1 0
Χγ
F
160
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
430 ΧΥ Example 5, Colorless Gel
0 Step 2
OH x>^ . F
yY 0 ch3 ΥΥΥ
H II I
y Y '' zY
N r Ό' I
0 ch3 O-
YY ch3
Ay
431 ΧΥ Example 5, Colorless Gel
0 Step 2
OH
yY 0 ch3 Y ZY
H II 1
Zs γ Y '' Y
N r V T
0 ch3 Y ch3
Ay
432 ZX Example 5, Colorless Gel
0 Step 2
.OH
Ai 0 ch3 AY
H II
Zs x n„, Y yY Y
N r o'
0 ch3 xr
Yz A ch3
Ay
F
161
2019201931 20 Mar 2019
Figure AU2019201931A1_D0069
162
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
436 H3Y Example 5, Colorless Oil
0 Step 2
YY- /OH 0 ch3 A/CH3
H II i
y γ k, A a '' Yy
N r 0^ \Y
0 ch3
YY k ch3
Yy
F
437 H3Y Example 5, Colorless Oil
0 Step 2
YY xoh 0 ch3 <ych’
H II 1
y γ N,„ Yk Y Yy
N r 0^
0 ch3 ΥΥ /CH3
Yy
F
438 h3Y Example 5, Colorless
0 Step 2 Foam
.OH
yY 0 ch3 Yk
H II
y / -Nzz, Y Yy
N r 0 I
0 ch3
ya CH3
Yy
F
163
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
439 AX Example 5, Colorless
0 Step 2 Foam
OH z<\ > F
Al 0 ch3
H II
k\ S N,„ X Xx
N r Ό 1
0 ch3 XX ch3
\a
F
440 ΆΧ Example 5, Colorless Oil
0 Step 2
OH F
Al 0 ch3 χ^χ
H II 1
N,„ X χΧ
N r V X,—
0 ch3 /CL
XX Xh 3
χχ
F
441 ΆΧ Example 5, Colorless Oil
0 Step 2
OH /X / F
ri 0 ch3
H II I
J N„, X Xx
N r Ό \Z
0 ch3 ffft /CH3
px
F
164
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
442 H3% Example 5, Step 2 White Foam
A Αν ^OH H \zN o 0 ch3 00 00+ 'CH3
O ch3
h3cA 0^x
443 Example 5, Step 2. White Foam
A N °H 00- ch3 -9
0 CH0°' . ch3
0
F
444 H3% Example 5, Step 2. White Foam
A / N 0H 00- ch3 9
0 CH0°' 1 F
0
F
165
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
445 h3A Example 5, White Foam
0 /OH , F Step 2.
Xv 0 ch3 yy
X X N γΧ X, /
o ch3h3c yy ch3
xy
F
446 h3A Example 5, White Foam
0 /OH , F Step 2.
X|f 0 ch3
X ΑΝ y/s X, /
o ch3h3c yy F
A
F
447 h3A Example 5, White Foam
0 /OH Step 2
d 0 ch3
H II
X s K/n6, Λ Xa
N Π 1 o^V
0 ch3 fX A
X
ch3
166
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
448 H3C+_ Example 5, White Foam
o I Step 2
.OH /N .F
Y o CH3 Y |T Y
H II i
A X A / n x,, Y^· xA . A γ
N Y ( o' .·' ^<Y
o ch3 Fx
Ail
kY
ch3
449 H3C+_ Example 5, White Foam
O I Step 2
X .OH xCH3
o ch3 rA
H ||
Y- + χΝλ A. A .>>Ύ
N Y r Y
O ch3 F^
kY
ch3
450 H3<A Example 5, White Foam
O I Step 2
X .OH /n .F
Y o CH3 Y |T Y
H || i
A X A/N x,, Y^· xA .
N Y ( O' 1 I
o ch3 Fx AA CHs
ch3
167
2019201931 20 Mar 2019
Figure AU2019201931A1_D0070
168
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
454 Example 5, White Foam
0 I Step 2.
.OH 0 oh3 ay
H II i
γ X x /Ϋ X YyX
N T f °
0 ch3 Aii
yX
455 h3Y Example 5, White Foam
0 OH Step 2.
X 0 ch3 X Y
|l H II
¥ N',,X Y\ Υγ Y
N'
0 ch3 1
An
yX
ch3
456 h3Y Example 5, White Foam
0 χΟΗ Step 2.
Y\ 0 CH3 AXY
H II I
¥ Y ¥n Yk xk. -ΆΑ
N 1 0
0 ch3
Ail
yX
ch3
169
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
457 Example 5, White Foam
o OH Step 2.
y o ch3 YY
|l H II Ϊ
A N. ΥΑ Λ AJ1
N' γ ο γ
o CHs xk
\ π
kA
F
458 h3cy Example 5, White Foam
0 Step 2.
Yy .OH x^ xCH3 o ch3 YYY
H
Y A- χΝ Yk Y\ A/
N γ ο γ·
0 CH3 xk
\ ll
kA
F
459 h3cy Example 5, White Foam
0 χΟΗ /x . F Step 2.
Air o ch3 YYY
H
γ Y \.N /,, kk A. YA
N 1 0 I I
0 CH3 xk F
V ll
kA
170
2019201931 20 Mar 2019
Figure AU2019201931A1_D0071
171
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
463 o /-ch3 Example 6B. Slightly Opaque Colorless
Viscous Oil
gX 0 CH3 XX< , Γ
H II :
X Jk S \XaX
N Ϊ 1 °
0 ch3
χχ
F
464 H3¥ 0<yCH3 /° Example 6B. Yellow Oil
0 ( .0 ^F
fiS r o ch3 <
H || 1
X - k¥,A s
N ¥ 1 0
0 ch3h3c. CH3
F
465 o^ch3 Example 6B. Clear, Colorless Oil
<° CH 3
1 ch3
.0
flf o ch3 ch3
H II !
A /X
N Y 1 0 i
o ch3 A
Y
X
η3Α c \h3
:h3
172
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
466 O^CHa Example 6B. Pale Yellow Oil
X r° ch3
.0 Y 0 CH 3 A XYh3
H II I
Y / ΚχΝ, A X sAy A
N γ χθ
0 CH, .
γ il
AY
h3Y X3
467 0<yCH3 Example 6B. Pale Yellow
Oil
r° ch3
.0 xX /CH3
Ai Y o ch, r
H II
Y / XyX A X
N Π 1 °
0 ch3
Ail
AX
h3X ch3
468 H3C 0<yCH3 Example 6A. Fluflfy White
0 Powder
χθ
d 0 ch3 γYy
H II
Y X/Y, Xs x XX
N' Π 1 0
0 CH3H3Cx γΧ ch3
A^
F
173
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
469 HX r A N ΟγΟΗ3 1 H Az M,„. 0 A o / YA< CH3 JXCH3 Xh3 Example 6A. Clear, Colorless Oil
0 ch3 A
A
h3A Ah3 :h3
470 HX ΟγΟΗ3 ch3 Example 6A. Clear, Colorless Oil
A A N' .0 iT^' 0 Λ ch3 '0^ O Xh3
0 ch3 Y
H3cA Ah3
471 0<yCH 3 ch3 Example 6A. Clear, Colorless Oil
A N 0 H YYN/' λΑ x^CH3
0 ch3 Aa
η3<τ Ay
ch3
174
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
472 h3® °γ( /° :h3 Example 6B. White Foam
o A UH3
/° o.
Yif o ch3
X X N γΧ xY
O ch3
h3cX r k
k k
F
473 H3C V /O zH3 Example 6B. Sticky Wax
o Y /°
Xv o ch3
X JJs N Λ XX
O F— — F γ
γ
474 ΟγΧ Example 6B. Colorless Oil
H3® A
0 Y
0 ch3 YY
X . N Y^Y
- ch3
0 ch3 X
A
175
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
475 h3Yo o^ch3 CH 1 3 Example 6A. White Foam
CL F
fikk ° CH 3 A^
Η II
N '< 0 Ύ/
0 ch3 ch3
Ax
F
476 <ycH3 hy <° Example 6B. White Foam
x° o ch3 a
kyy Αγ J
0 ch3
a |1
A s
477 h3Yq o^ch3 XN Example 6A. White Foam
γΥ
rY o ch3 AA
k A/kA / yA
n ·< °
0 ch3
A
A jj
1 r 1 4
176
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
478 H3k °<γΟΗ3 Example 6A. White Foam
0 V
A Y/O 1 H 0 || ch3 ΑγΛ F
k /k/N,„ A \ χ xkA
N 0
0 ch3 k
k
1 Γ
479 A 0<yCH3 0 Example 6A. White Foam
.0 k o ch3 k hkkk^CHs
H II
kk. k xk
N Ύ r 0 ch3
k h
k
Nk ch3
480 h3c^ o^ch3 /° Example 6B. White Foam
0 r 0
,0 T 0 ch3 k YokY
H II
kN,k xk
N Ό'
0 ch3
A 'll
k
CD xck ch3
177
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
481 0<yCH3 r° Example 6B. White Foam
h3C.o ch3
k k N c ch3 ) XX ci
0 0H3 /Ox h3c Γ
Cl
482 H3% O<yCH3 H 3γ Example 6B. White Foam
kl k k N kA ch3 1 A XX X^x F
o ch3 .cl r ch3 A k
X L
483 °<yCH3 H A Example 6B. White Foam
aXi k k N XvX CL ch3 X A/ Cl
0 ch3 .ox r ch3 V
X
Cl
178
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
484 h3c 0<yCH3 0 H3C γ Example 6B. White Foam
0 A A
Ai χθ CL Y o ch3 YX^CH3
Y xN 0 CH3 .CL r z ch3 yY A
zA
ch3
485 XyCH3 n Example 6A Colorless Oil
Y\ a
ZA o ch3 Ay
H II
ks Υ/Υ Yk x AY
l\T Π 1 0
o ch3
rYk
Ay
F
486 H3C'O ch3 1 Example 6A Colorless Oil
.0
V Zr o ch·, < Χγ
H || 1
ks k/N, A Y xY
N' if 1 0
0 CH3H3C- ch3
γΥ
h3c χθ
179
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
487 O^CH3 /° Example 6B Colorless Oil
O ( o
. /O /A /F
A ii 0 CH 3 rTT
H II
¥ A^/N/z, - .GaG
N [f f 0
0 ch3
A
HG A g
F
488 Η3% o^ch3 Example 6A. White Foam
.0 Xx
γ O CH 3 GV ¥h3
H || I
¥ A/¥ Ax A AX
N Π 1 0
0 ch3 „ Ox
Ti A T CH3
N A
Ox. ch3
489 H3C.0 o^ch3 X /x XH3 Example 6A. White Foam
vr 0 ch.
H II
AaA > G\G
N Ϊ 1 0
0 ch3 o h3c ¥ if A °ch3
to
ch3
180
2019201931 20 Mar 2019 *Cmpd.
No.
Structure
Prepared
According
To
Example
Appearance
490
Figure AU2019201931A1_D0072
Example 6A.
White Wax
491
Figure AU2019201931A1_D0073
Example 6A.
White Foam
492
Figure AU2019201931A1_D0074
Figure AU2019201931A1_D0075
Figure AU2019201931A1_D0076
Example 6A.
White Foam
181
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
493 %^ch3 Example 6B White Foam
H3% r 0 /CA ch3 0
0 1 I o. A
A 0 ch3 π
| H II
A N„, As Xa
Ν' 0 1 ch3 ox <A
h3A r k
X
0 I
CH 3
494 °S ch3 Example 6C White Foam
A CH 3
h3c 0 ... _AH3
0 CH3 u
-0 0. A
0 ch3
I H II
ks NZ.X Xa
N' A
0 ch3
XA ch3
X\
0
I ch3
495 Y °A ch3 /CH3 ch3 0 1 1 Example 6A White Foam
0 0. A
A 0 ch3 π
|l H II
A N,„. X XaX
N' A
0 ch3 L /A
XA ch3
X
' 0
I ch3
182
1002492809
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According to Example Appearance
496 h3cx o^ch3 Example 6A White Foam
0 ch3 1 3 ch3
A CL
X X 0 ch3 Y γχ
H II
k XX„ kk . X
N' Π 1 0
0 ch3 Xk /CL ch3
Ύη3
497 h3cl o^ch3 Example 6A Colorless
o Film
X o ci-k r X
H II
k X/N,„ A > y\ l
L Π 1 ° γ 0
O CH3H3C x. ch3
Q>
ch3
498 h3c^ o^ch3 Example 6A. White Foam
0 ch3 1 F
A CL /k M
J 0 ch3 Y
H II
k ΧγΆ Z X
N' Π 1 0
0 ch3 .0.
iik Y x3
t
F
183
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
499 h3c^q o^ch3 ch3 Example 6A. White Foam
K il O ch3 J Ια X A. N rT i ° kk
o ch3h3c^xX CH3
Xz ^ch3
500 h3c^o o^ch3 Ia / r nr ° ch3 k k ly, a Ak N ίΤ k 0 ΊΓ <y/CH3 Example 6A. White Foam
o ch3h3c^X ch3
ch3
501 h3cxo o^ch3 F Example 6A. White Foam
// S. /^ K iT O CH3 ζ lA Λ A N kk k ° fl! XX
O CH3H3C\xX ch3
502 H3C^o ΟγΟΗ3 /X/° A/X- k¥ h g A Xo/CH3 Example 6A. White Foam
o ch3 K r?i
kA ch3
184
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
503 0<yCH3 ch3 1 Example 6A. White Foam
sO F.
0 Yr o CH 3 \Y γ
H II
A 0/
N' Π 1 °
0 ch3 f>
Y
0 p
0 Vh3
504 h3A °<yCH3 Example 6A. White Foam
0 ?H= \ .F
sO o
0s Yr o H II CH 3 >ΑΑγΛ F
A Y00
N' Π 1 0
0 ch3 . .0.
y VY ch3
Y 0
Γ F 1
505 HsC. O<yCH3 Example 6A. Clear,
O F Colorless Oil
0 AJ Ά o ch, Y0
H II
A γΛ .Υ
N if 1 °
o ch3
0s ΪΊ
0 u \ /CHs
o
185
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
506 H;C'o °γΟΗ3 HA Example 6A. Clear, Colorless Oil
X N' A' ch3 An A'™’
o ch3 Jl
h3c A' X/ YCH3
507 H’c'o o^ch3 ch3 Example 6A. Clear, Colorless Oil
X N' y ° if X' ch3 ^Ao-CH3
0 ch3 AA
H3cY -XA Xh=
508 H3Cy X . N O^CH, kJ/ X' ch3 y^CH3 UYo.CH3 Example 6A. Clear, Colorless Oil
o ch3 Jl
XA Xh’
CH;
186
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
509 h3A o^ch3 Example 6A. Clear,
0 Colorless Oil
/0 n
A o ch3 ya ch3
H II
A YNY /Λ
N' o' “F
o ch3
AY
Xa Y
ch3
510 H3A o^ch3 Example 6A. Clear,
O Colorless Oil
n o^
Y A o ch3 /A ch3
H II
Yn„, A AaS
N' if 1 o ch3 o' ch3
AY
XX Xh3
A ch3
511 A o^ch3 ch3 1 Example 6A. Clear,
O Colorless Oil
.0 o.
Y^ A o ch3 AY
H II
Yn,A . xCH3
N' if 1 o' o
o ch3 rY· 1 Cl I3
h3c. Xy>
o'
187
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
512 AX O^CH3 Example 6A. Clear,
0 Colorless Oil
.0 T 0 h3c. ch3 γΧ
H II
kx . ¥ /A, X xX /CH3
N ¥ i Ό'
0 CH3H3C. -X X
¥CH3
513 ΟγΟΗ3 Example 6B. Clear, Colorless Oil
AX /°
0 f F
r . /0 T 0 ch3 X,
H II
Lx. X/A, X Ό ΧΧχΗ3
N if 1 0 ch3
Xs
X^ P/CH3
F' 0
514 o^ch3 Example 6B. Clear, Colorless Oil
H3% r° H3%
rX . /0 T 0 ch3 r¥l
H II
A X/A, X O' XXXA
N If 1 0 ch3
X
h3c. P/CH3
O' 0
188
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
515 °γ£Η3 Example 6B. Clear, Colorless Oil
H=c'o r° ch3
AY /0 r o ch3 All
H II
¥ Y yY X /CH3
N Y r 0 ch3 Yr 0
Ai
¥ /CH3
h3c 0
516 ΟγΟΗ3 Example 6B. Clear, Colorless Oil
Η3¥ /°
0 .0 ch3
γ¥ T 0 ch3 X
H II
¥ / ¥/Nz, Y γγγ /CH3
N Y r o ch3 '0' 0
Ay
L .CH 0 3
ch3
517 o^ch3 Example 6B. Clear, Colorless Oil
h3c /°
0 Γ /0 .Ck
Air 0 ch3 AXr ch3
H II
¥ Y \/Nzz, X
N Y r 0 ch3 ''o' ¥
X/
CY ch3
189
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
518 OyCH3 Example 6B. Clear, Colorless Oil
H3C. x°
0 Γ O .0^
rii Γ 0 ch3 Αγ ^ch3
H II
Y > Y χΝ,„ Y A AY
N τ r 0 ch3 o' ch3
jj
Υχ oh3
Οχ ch3
519 o^ch3 Example 6B. Clear, Colorless Oil
r° CH 3
n Ox
Yy Γ 0 ch3 YY
H II
Y 2 Y.n„, A A^Y./CH3
N o' -0
0 ch3 χθ>
h3c- -Y
Ax kyH3
520 °γΟΗ3 Example 6B. Clear, Colorless Oil
h3C /0
0 (
YY .0 ' 0 H?Cx CH3 A
H II
Y 7 \/νΆ YAY xCh3
N π T o' -0
o ch3h3c. A
Ax lf0.CH3
190
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
521 HsC-o O<yCH3 .o HsC-O F Example 6A. White Foam.
It o ch3 y Y''
k+ . N ΐγΝ^Λ ό ^χΧ
o ch3 Av O+Hs
AY
F
522 A °+/CH3 y h3c Example 6A. Sticky White Foam
.0 ,F
Y ch3AA
k· x N γΑ- -YYa Y
o ch3 klY Xox Ah3
AY
F
523 H3+O 0<yCH3 Example 6A Colorless Oil
Y A 0 ch3 A A
H II 1
A A A . +A .to <+ Y
N if 1 o y γ
0 ch3 0 Ah3
AY
191
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
524 HY 0<yCH3 zO zF Example 6A Colorless Oil
X T o CH3 XlT
H II
A Χγ,, A z X <'X y
N Π 1 0 1 1
0 ch3 JA ch3
Ay
525 H=c'o °<yCH3 Example 6A Colorless Oil
γΑ zO Y 0 CH3 XX
H II
A z Α/ΥΛ z AA/
N Π 1 0
0 ch3 zX Y
A y ch3
kJ
F
526 H% 0<yCH3 Example 6A Colorless Oil
x \ zO ii 0 CH3 XX
H II
A X zNz, X X ,A A
N π T 0 ι
o ch3 XzCh3
F
192
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
527 H3C O^CH3 Example 6A Colorless
0 Foam
/0
IT 0 CH3 YY
H II
X Ax Yk Ϋ. .YY
N if 1 0 J[ 1
0 ch3 A °XCH3
YY
ch3
528 h3<® o^ch3 Example 6A Colorless
0 Foam
/0
rY it 0 CH3 XV
H II
X Ax A zY . Y J
N [f 1 0 1 I
0 ch3 Υχ CHs
ch3
529 h3® o^ch3 Example 6A Colorless
0 Foam
/0 /CH3
T 0 ch3 yx
H II I
X s Y/N^YX / Y YY
N X f 0
0 ch3 X\ ζ<λ
YY ch3
YY
F
193
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
530 h3Y °ks/CH3 Example 6A Colorless
0 Y Foam
χθ xCH3
T 0 ch3 { z\/ ύ
H II II
Y X X/Y XY / yX
N Π 1 0
0 ch3 χχ xCH3
Xy
F
531 0<yCH3 Example 6A Colorless Oil
χθ
Xs ΠΓ 0 ch3 <y yy
H II I
Y Χυ,Λ xY '' yX
N Π f ° 1
0 ch3 Ύ
Xy ch3
Ay
F
532 °γΥ Example 6A Colorless Oil
χθ
rX it 0 ch3 Υγγ
H II J
Y ΥΧ/Ν/,,ΧΥ X '' yX
N ff 1 0 I
0 ch3 χγ ch3
Ay
F
194
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
533 0<yCH3 Example 6A Colorless Oil
zO , F
7r o ch3
H II I
X /k A άΑ
i\T Ϊ 1 °
0 ch3
X ch3
XX
F
534 0<yCH3 Example 6A Colorless Oil
zO , F
A τ o ch3 A
H II I
X X/N%Ak /k A άΑ
N Π f 0
0 ch3 Xa, /CH3
F
535 h3c^h3c^o Example 6A. White Foam
fl z'-' r o ch3
H II |l
A J· k/N,„X / /AX ^A\
N Π 1 ° ch3
o ch3
fil
XY
h3c¥
195
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
536 Ύ O^CHa Example 6A. White Foam
χθ F
J 0 ch3 Ay
Y N' ΧγΥΥ
0 CH3 .Ox h3Y γΑ x ch3
A,
F
537 Ύ %^CH3 Example 6A. White Foam
χθ F
r J 0 ch3 Ay
Y N' ΧγΥΥ
0 CH3 .Ox 1 F
h3Y γΑ
A
F
538 Ύ %^CH3 Example 6A. White Foam
χθ F
r J 0 ch3 Ay
Y N' ΧγΥΥ
0 CH3H3Cx γΑ 1 \ Y Y CH 3
A
F
196
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
539 Χθ o^ch3 Example 6A. White Foam
vk A vkX .F
Xlk 0 ch3 r ii
A N X 0 a.....y
0 ch3h3c 1 M F
xy
F
540 Example 6A. White Foam
χ^γ° ° ch3 X 7i
H II
k k\/N/„k\ X. ,,-ά
N Π 1 o X
0 ch3 κ /X
A η
xy
ch3
541 Η3ΑθΗ3ο^ο Example 6A. White Foam
vk A /χ .F
X/ 0 ch3 r if
Η II i
k kk/N„, A X\ aXX
N ϊΓ i 0 X.·' X.—
0 ch3 f. \X
xy
ch3
197
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
542 h3c, h3c 3 k ¥° Example 6A. White Foam
,ch3
Ay 0 ch3 k k
H II I
k A ¥<N/ Ak A AA
N (
0 ch3
Aii
kA
ch3
543 h3c^oh3c^o Example 6A. White Foam
0 _F
A 0 ch3 Ad k
H || i
k / Ak γ A xk y'AA
N γ O' 1 I
0 ch3 Fx TkA CHs
¥k
ch3
544 h3c^oh3c^o Example 6A. White Foam
0 /n .F
A 0 ch3 Ad k
H II
k / Ak , A A, yAA
N γ O' 1 I
0 ch3 F> Y YY F
NY k
kk
ch3
198
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
545 HX 0<yCH3 Example 6A. White Foam
/0 /Ox XX
yA d 0 CH3 gGG
H II
A s A/X, GY / A - AG
N Π 1 0
0 ch3 gG
GG
546 XX 0 °Ύ°Η3 Example 6A. White Foam
Af o CH3 gG
H II
A /A/X. GY A GaG
N Π 1
0 ch3 1
¥ N
aG
ch3
547 X °<yCH3 Example 6A. White Foam
X /0
A iT 0 CH3 GGG
H II I
¥ Ax, GY A GaG
N if I 0
0 ch3
gGi
aG
ch3
199
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
548 o o^ch3 Example 6A. White Foam
Xv o CH3 AX
H II
γ .AX
N Y 1 o y
o ch3
An
xA
F
549 HsCx O<yCH3 Example 6A. White Foam
.o />, /CH,
ΐτ O CH3 aYA
H II
X . X/Χ AY / X .. XX
N Π 1 °
o ch3
An
XX
F
550 HX XyCH3 Example 6A. White Foam
X ιΤ O ch3 AXA
H II
X X\ /X, Αχ .XX
N Π I 0 1 1
0 ch3 F
An
XX
200
2019201931 20 Mar 2019
*Cmpd. No. Structure Prepared According To Example Appearance
551 H3% O<yCH3 Example 6A. White Foam
.o .F
A Zf O chs γ γ
H II ϊ
γ \/νΎ A
l\T Π 1 o' 1 I
o ch3 A F
Γ ll
xA
ch3
552 H3% O<yCH3 Example 6A. White Foam
.o .F
Zf O chs A if
H II ϊ
γ xY X A A .YY
l\T Π 1 Ό 1 I
o ch3 A F
0 ll
xA
F
553 h3X cw.ch3 Example 6A Colorless
0 Ύ ch3 Foam
.F
A Zf O CH3 A |f
H II 1
Y χΥ /Ν,,, A A.
N' Π 1 o
0 ch3
f|X
Aa
201
2019201931 20 Mar 2019
Figure AU2019201931A1_D0077
*Cmpd. No. - Compound Number
202
2019201931 20 Mar 2019
Table 2. Analytical Data
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
1 ... ... HRMS-ESI (m/z) [M]+ calcd for C23H29NO5, 399.2046; found, 399.2048 1H NMR (500 MHz, CDC13) δ 7.53 7.41 (m, 4H), 7.32 - 7.23 (m, 4H), 7.23 7.13 (m, 2H), 6.01 (q, J= 6.3 Hz, 1H), 4.98 (d, 5= 8.0 Hz, 1H), 4.13 (p, J= 7.1 Hz, 1H), 2.78 (s, 1H), 1.41 (s, 9H), 1.21 (d, J= 6.3 Hz, 3H), 0.83 (d, J= 7.3 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.55, 154.95, 145.04, 142.86, 128.32, 128.30, 127.17, 127.11, 125.59, 125.52, 79.83, 79.54, 75.16, 49.13, 28.29, 17.95, 14.38
2 ... ... ESIMS m/z 384.5 ([M+H]+) Ή NMR (400 MHz, CDC13) δ 7.42 7.07 (m, 10H), 5.80 (dq,5= 10.1, 6.1 Hz, 1H), 4.97 (d, J= 8.0 Hz, 1H), 4.19 - 4.06 (m, 1H), 4.03 (d,5= 10.1 Hz, 1H), 1.41 (s, 9H), 1.23 (d,5= 6.1 Hz, 3H), 0.76 (d, 5=7.2 Hz, 3H) 13CNMR(101 MHz, CDCI3) δ 172.83, 154.96, 141.52, 141.26, 128.79, 128.50, 128.10, 128.08, 126.91, 126.67, 73.10, 57.98,28.33, 19.31, 17.98
3 ... - ESIMS m/z 396.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.22 7.15 (m, 2H), 7.00 (ddd,5= 3.5, 1.2, 0.6 Hz, 1H), 6.97 - 6.89 (m, 3H), 5.52 (dq, J = 7.3, 6.2 Hz, 1H), 4.99 (d,5=5.1Hz, 1H), 4.63 (d, 5= 7.3 Hz, 1H), 4.29 - 4.18 (m, 1H), 1.43 (s, 9H), 1.28 (d, 5= 6.2 Hz, 3H), 1.04 (d, 5= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.64, 143.87, 142.87, 126.75, 126.55, 125.98, 125.39, 124.58, 124.56, 79.69, 74.40, 49.31,47.46, 28.32, 18.74, 18.22
203
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
4 ... ... ESIMS m/z 420.6 ([M+H]+) 1H NMR (400 MHz, CDC13) 57.317.16 (m, 4H), 6.97 (td, J= 8.7, 7.0 Hz, 4H), 5.71 (dq, 7=9.8, 6.1Hz, 1H), 4.95 (d, J= 8.0 Hz, 1H), 4.22 - 4.07 (m, 1H), 4.03 (d, 7= 9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 0.84 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -115.53,-115.94
5 ... ... ESIMS m/z 450.6 ([M+Na]+) 1H NMR (400 MHz, CDC13) δ 7.37 7.19 (m, 10H), 6.01 - 5.89 (m, 1H), 5.02 (d, 7= 7.9 Hz, 1H), 4.27-4.10 (m, 1H), 3.38 (dq, 7= 8.9, 6.9 Hz, 1H), 3.25 3.13 (m, 1H), 1.40 (d, 7= 2.1 Hz, 9H), 1.18 (t, 7= 7.0 Hz, 3H), 1.15- 1.06 (m, 6H)
6 ... ... ESIMS m/z 436.6 ([M+Na]+) 'H NMR (400 MHz, CDC13) δ 7.38 7.21 (m, 10H), 6.01 - 5.82 (m, 1H), 5.01 (d, 7= 8.0 Hz, 1H), 4.27-4.12 (m, 1H), 3.15 (s, 3H), 1.40 (s, 9H), 1.15 - 1.07 (m, 6H)
7 ... ... ESIMS m/z 456.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.36 (td, J = 8.5, 6.1 Hz, 1H), 7.26 - 7.15 (m, 1H), 6.91 - 6.68 (m, 4H), 5.86 - 5.73 (m, 1H), 4.92 (d, 7= 8.0 Hz, 1H),4.66 (d,7= 10.1 Hz, 1H), 4.23 - 4.09 (m, 1H), 1.42 (s, 9H), 1.27 (d,7=6.1Hz, 3H) 19F NMR (376 MHz, CDC13) δ -111.06 (d, 7= 7.6 Hz),-111.55 (d,7= 7.5 Hz),-111.91 (dd, 7= 7.9, 2.7 Hz), 112.72 (d, 7= 5.9 Hz)
8 ... ... ESIMS m/z 424.5 ([M+Na]+) 1H NMR (400 MHz, CDC13) δ 7.48 7.41 (m, 4H), 7.38 - 7.19 (m, 6H), 5.97 (dq, 7= 25.6, 6.5 Hz, 1H), 4.90 (d, 7= 7.8 Hz, 1H), 4.23 - 4.05 (m, 1H), 1.41 (s, 9H), 1.29 (dd,7=6.5, 1.0 Hz, 3H), 0.75 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -169.03
204
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
9 ... ... ESIMS m/z 444.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.22 7.09 (m, 4H), 6.91 - 6.65 (m, 4H), 5.70 (dq, J= 9.8, 6.1 Hz, 1H), 4.94 (d, 7=8.0 Hz, 1H), 4.19 -4.05 (m, 1H),3.93 (d,7= 9.8 Hz, 1H), 3.76 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.21 (d, 7= 6.2 Hz, 3H), 0.83 (d,7=7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.84, 158.34, 158.22, 133.99, 133.81, 128.96, 114.10, 113.84, 79.64, 73.33, 56.17, 55.22, 49.22, 28.31, 19.28, 18.19
10 ... ... ESIMS m/z 420.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.33 7.21 (m, 2H), 7.14 - 7.02 (m, 2H), 7.03 6.84 (m, 4H), 5.72 (dq, 7= 9.9, 6.2 Hz, 1H), 4.93 (d, 7= 8.0 Hz, 1H), 4.22 - 4.07 (m, 1H), 4.03 (d, 7= 9.8 Hz, 1H), 1.42 (s, 9H), 1.24 (d, 7= 6.2 Hz, 3H), 0.84 (d, 7= 7.1Hz, 3H) 19F NMR (376 MHz, CDC13) δ -112.14,-112.59
11 ... ... ESIMS m/z 452.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.33 7.11 (m, 8H), 5.71 (dq,7= 10.0, 5.9 Hz, 1H), 4.94 (d, 7= 8.0 Hz, 1H), 4.18 - 4.07 (m, 1H), 3.99 (d, 7= 9.9 Hz, 1H), 1.42 (d, 7= 1.7 Hz, 9H), 1.24 (d, 7= 6.2 Hz, 3H), 0.87-0.81 (m, 3H) 13C NMR (101 MHz, CDC13) δ 172.79, 154.94, 142.68, 142.43, 134.73, 134.43, 130.21, 129.93, 128.39, 128.32, 127.49, 127.18, 126.28, 126.20, 79.79, 72.40, 57.09, 49.15,28.30, 19.21, 18.04
12 ... ... ESIMS m/z 382.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.79 7.72 (m, 2H), 7.72 - 7.62 (m, 1H), 7.59 7.48 (m, 1H), 7.46 - 7.36 (m, 2H), 7.36 7.25 (m, 2H), 5.81 - 5.64 (m, 1H), 5.09 (s, 1H), 4.55 - 4.34 (m, 1H), 4.33 - 4.18 (m, 1H), 1.46 (s, 9H), 1.45 (d, 7= 3.5 Hz, 3H), 0.70 (d, 7= 6.3 Hz, 3H)
205
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
13 ... ... ESIMS m/z 398.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.33 7.21 (m, 4H), 7.15 - 7.04 (m, 4H), 5.15 5.03 (m, 1H), 5.01 (d, J = 8.0 Hz, 1H), 4.35 - 4.24 (m, 1H), 4.27 - 4.15 (m, 1H), 1.44 (s, 9H), 1.29 (d, J= 7.2 Hz, 3H), 1.03 (d, 7=6.4 Hz, 3H)
14 ... ... ESIMS m/z 542.5 ([M+H]+) Ή NMR (400 MHz, CDC13) δ 7.46 7.36 (m, 4H), 7.17 - 7.07 (m, 4H), 5.71 (dq, J= 9.7, 6.2 Hz, 1H), 4.91 (d, J= 7.9 Hz, 1H), 4.13 (p, J= 7.2 Hz, 1H), 3.97 (d, J= 9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d, J= 6.1 Hz, 3H), 0.86 (d, J= 7.2 Hz, 3H)
15 ... ... ESIMS m/z 424.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 6.73 (d, J = 3.4 Hz, 1H), 6.67 (d, J= 3.4 Hz, 1H), 6.59 - 6.46 (m, 2H), 5.43 (dq, J= 7.4, 6.2 Hz, 1H), 5.03 (d,7=8.1 Hz, 1H),4.42 (d, 7= 7.3 Hz, 1H), 4.24 (p,7= 7.1, 6.7 Hz, 1H), 2.41 (d,7= 1.1 Hz, 3H),2.40 (d,7= 1.1 Hz, 3H), 1.43 (s, 9H), 1.27 (d, 7= 6.2 Hz, 3H), 1.09 (d, 7=7.1 Hz, 3H)
16 ... ... ESIMS m/z 412.6 ([M+H]+) Ή NMR (400 MHz, CDC13) 5 7.187.11 (m, 4H), 7.11-7.02 (m, 4H), 5.75 (dq, 7= 10.2, 6.2 Hz, 1H), 4.95 (d, 7= 8.0 Hz, 1H), 4.11 (p, 7=7.4, 6.5 Hz, 1H), 3.95 (d, 7= 10.0 Hz, 1H), 2.27 (s, 3H), 2.25 (s, 3H), 1.41 (s,9H), 1.22 (d,7=6.1 Hz, 3H), 0.80 (d, 7= 7.2 Hz, 3H)
18 ... ... ESIMS m/z 452.6 ([M+H]+) Ή NMR (400 MHz, CDC13) δ 7.55 (d, J = 8.1 Hz, 2H), 7.41 (d, 7= 8.0 Hz, 2H), 7.31 - 7.16 (m, 5H), 5.82 (dq, 7= 9.9, 6.2 Hz, 1H), 4.92 (d, 7= 7.9 Hz, 1H), 4.15 4.06 (m, 2H), 1.41 (s, 9H), 1.24 (d,7= 6.2 Hz, 3H), 0.77 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -62.58
206
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
19 ... ... ESIMS m/z 452.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.30 7.22 (m, 4H), 7.22 - 7.15 (m, 4H), 5.71 (dq, J= 9.6, 6.2 Hz, 1H), 4.91 (d, J= 8.0 Hz, 1H), 4.21 - 4.06 (m, 1H), 4.00 (d, J= 9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d,/= 6.2 Hz, 3H), 0.85 (d, /= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.75, 154.96, 139.41, 139.25, 133.03, 132.77, 129.43, 129.35, 129.05, 128.74, 79.81, 72.51, 56.45, 49.17, 28.30, 19.18, 18.09
20 ... ... ESIMS m/z 406.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.25 7.14 (m, 4H), 7.06 - 6.87 (m, 4H), 5.68 (dq, /= 9.3, 6.2 Hz, 1H), 4.83 (s, 1H), 4.02 (d, /= 9.3 Hz, 1H), 3.82 (dd, /= 18.2, 5.9 Hz, 1H), 3.56 (dd,/= 18.2,5.2 Hz, 1H), 1.43 (s, 9H), 1.22 (d,/= 6.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 169.66, 161.74 (d,/= 245.9 Hz), 161.63 (d,/= 245.7 Hz), 155.45, 136.74, 129.65 (d,/= 7.9 Hz), 115.70 (d,/= 21.3 Hz), 115.41 (d, /= 21.2 Hz), 79.97, 77.21, 73.15, 55.84, 42.44, 28.29, 19.17
21 ... ... ESIMS m/z 434.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.30 7.15 (m, 4H), 7.06 - 6.89 (m, 4H), 5.75 5.62 (m, 1H), 4.90 (d, /= 8.4 Hz, 1H), 4.11 (q,/= 6.7 Hz, 1H),4.O3 (d,/= 9.8 Hz, 1H), 1.49 - 1.33 (m, 10H), 1.30 1.08 (m, 4H), 0.54 (t, /= 7.4 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 172.10, 161.70 (d, /= 245.6 Hz), 155.20, 136.97, 129.52, 115.71 (d,/=21.3 Hz), 115.44 (d, /= 21.2 Hz), 79.73, 73.12, 56.08, 54.46, 28.30, 25.40, 19.26, 8.95
207
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
22 ... ... ESIMS m/z 448.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.30 7.15 (m, 4H), 7.04 - 6.91 (m, 4H), 5.69 (dq, J= 9.7, 6.1 Hz, 1H), 4.86 (d, J= 9.3 Hz, 1H), 4.09 (dd, J= 9.3, 4.2 Hz, 1H), 4.03 (d, 7= 9.8 Hz, 1H), 1.69- 1.57 (m, 1H), 1.42 (s,9H), 1.21 (d, 7= 6.2 Hz, 3H), 0.73 (d, 7= 6.9 Hz, 3H), 0.43 (d, 7= 6.8 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.77, 161.73 (d, 7= 246.0 Hz), 155.60, 137.05, 129.61, 129.52, 129.44, 115.71 (d,7= 21.6 Hz), 115.49 (d, 7= 21.4 Hz), 79.69, 73.23, 58.49, 56.03, 30.92, 28.28, 19.31, 18.96, 16.54
23 ... ... ESIMS m/z 462.7 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.30 7.20 (m, 4H), 7.04 - 6.92 (m, 4H), 5.68 (dq, 7= 9.8, 6.2 Hz, 1H), 4.72 (d, 7= 8.9 Hz, 1H), 4.10 (td, 7= 9.2,5.1 Hz, 1H), 4.02 (d, 7= 10.0 Hz, 1H), 1.41 (s, 9H), 1.22 (d,7= 6.1 Hz, 3H), 0.96 (ddd,7= 13.7, 9.6, 5.5 Hz, 1H), 0.84 (m, 1H), 0.75 (d, 7= 6.5 Hz, 3H), 0.70 (d, 7= 6.6 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 173.06, 161.72 (d, 7= 245.8 Hz), 155.29, 137.17, 136.83, 129.49, 115.73 (d, 7= 21.4 Hz), 115.46 (d, 7= 21.3 Hz), 79.74, 73.02, 56.27, 52.04, 41.48, 28.28, 24.41, 22.76, 21.53, 19.23
24 ... (Thin film) 3358, 2977, 1708, 1491, 1243, 1162, 1051, 1027 HRMS-ESI (m/z) [M+Na]+ calcd for C25H33NNaO6, 466.22; found, 466.2191 1H NMR (300 MHz, CDC13) δ 7.50 7.37 (m, 1H), 7.29 - 7.19 (m, 1H), 7.20 7.06 (m, 2H), 6.92 - 6.75 (m, 4H), 5.91 (dq,7= 10.1, 6.4 Hz, 1H), 5.03 - 4.97 (m, 1H), 4.98 (d, 7= 9.9 Hz, 1H), 4.22 4.04 (m, 1H), 3.84 (s, 3H), 3.76 (s, 3H), 1.41 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.82 (d, 7= 7.2 Hz, 3H)
208
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
25 ... (Thin film) 3368, 2978, 1707, 1597, 1488, 1156, 1043 HRMS-ESI (m/z) [M+Na]+ calcd for C25H33NNaO6, 466.22; found, 466.2193 Ή NMR (300 MHz, CDC13) 5 7.18 (dt, J = 11.8, 7.9 Hz, 2H), 6.89 (dq, J= 7.6, 1.5 Hz, 2H), 6.83 (dt, J= 4.0, 2.1 Hz, 2H), 6.71 (dddd, J= 10.7, 8.2, 2.6, 0.9 Hz, 2H), 5.77 (dq, J= 10.2, 6.1 Hz, 1H), 4.96 (d, J= 8.0 Hz, 1H), 4.20 - 4.01 (m, 1H), 3.96 (d, J= 10.3 Hz, 1H), 3.77 (s, 3H), 3.75 (s, 3H), 1.42 (s, 9H), 1.24 (d, J= 6.2 Hz, 3H), 0.79 (d, J= 7.2 Hz, 3H)
26 ... (Thin film)3368 2979, 1706, 1504, 1162, 1052 HRMS-ESI (m/z) ([M+H]+) calcd calcd for CfA i F2NNaO4, 470.2113; found, 470.2122 'H NMR (300 MHz, CDC13) 5 7.14 7.02 (m, 2H), 6.99 - 6.84 (m, 4H), 5.67 (dq, J= 9.8, 6.2 Hz, 1H), 4.95 (d, J= 7.9 Hz, 1H), 4.22 - 4.05 (m, 1H), 3.94 (d, J= 9.8 Hz, 1H), 2.20 (d, 7= 2.1 Hz, 3H), 2.19 (d, J= 2.2 Hz, 3H), 1.42 (s, 9H), 1.28- 1.17 (m, 3H), 0.86 (d, J= 7.2 Hz, 3H)
27 ... (Thin film) 3366, 2978, 1706, 1162, 1051 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H31Cl2NNaO4, 502.1522; found, 502.1533 Ή NMR (300 MHz, CDC13) 5 7.22 (dd, J = 4.6, 1.9 Hz, 2H), 7.13 (t, J= 7.9 Hz, 2H), 7.04 (ddd, 7= 7.6, 5.1, 1.9 Hz, 2H), 5.67 (dq, 7= 10.0, 6.2 Hz, 1H), 4.96 (d, J = 7.9 Hz, 1H), 4.22 - 4.05 (m, 1H), 3.91 (d, 7= 9.9 Hz, 1H), 2.31 (s, 3H), 2.29 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.0 Hz, 3H), 0.87 (d, 7=7.2 Hz, 3H)
28 ... (Thin film) 3285, 2979, 2107, 1702, 1501, 1160 HRMS-ESI (m/z) [M+Na]+ calcd for C27H29NNaO4, 454.1989; found, 454.1993 Ή NMR (300 MHz, CDC13) 5 7.45 7.37 (m, 4H), 7.26 - 7.18 (m, 4H), 5.75 (dq, 7= 10.0, 6.1Hz, 1H),4.91 (d,7= 7.9 Hz, 1H), 4.20 - 4.06 (m, 1H), 4.04 (d, 7= 9.9 Hz, 1H), 3.05 (s, 1H), 3.04 (s, 1H), 1.42 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.82 (d, 7=7.2 Hz, 3H)
29 ... (Thin film) 3362, 2964, 1712, 1510, 1163, 1053 HRMS-ESI (m/z) [M+Na]+ calcd for C22H37NNaO4, 462.2615; found, 462.2622 Ή NMR (300 MHz, CDC13) 5 7.22 7.16 (m, 4H), 7.13 - 7.03 (m, 4H), 5.76 (dq, 7= 10.2, 6.1 Hz, 1H), 4.95 (d, 7= 7.8 Hz, 1H), 4.17 - 4.02 (m, 1H), 3.96 (d, 7= 10.2 Hz, 1H), 2.67 - 2.45 (m, 4H), 1.41 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 1.21- 1.10 (m, 6H), 0.73 (d, 7= 7.2 Hz, 3H)
209
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
31 ... ... ESIMS m/z 402.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.32 7.20 (m, 6H), 7.20 - 7.14 (m, 1H), 6.97 (t, J= 8.7 Hz, 2H), 5.75 (dq, J= 10.0, 6.2 Hz, 1H), 4.92 (d, J= 8.0 Hz, 1H), 4.11 (t, J= 7.4 Hz, 1H), 4.02 (d, J= 10.0 Hz, 1H), 1.41 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.77 (d,7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.81, 161.71 (d, 7= 245.7 Hz), 154.94, 141.23, 137.03 (d, 7= 3.5 Hz), 129.56 (d, 7= 7.9 Hz), 128.59, 127.99, 126.82, 115.62 (d,7 = 21.3 Hz), 79.70, 72.94, 57.09, 49.16, 28.31, 14.13
33 ... ... ESIMS m/z 519.6 ([M-H2O]+) 1H NMR (400 MHz, CDC13) δ 7.58 (t, 7 = 2.1 Hz, 2H), 7.38 (dd, 7= 8.4, 3.9 Hz, 2H), 7.29 - 7.25 (m, 1H), 7.20 (dd, 7= 8.5, 2.2 Hz, 1H), 5.84 (q, 7= 6.2 Hz, 1H), 4.94 (d, 7= 7.8 Hz, 1H), 4.14 (t, 7= 7.4 Hz, 1H), 3.05 (s, 1H), 1.41 (s, 9H), 1.18 (d, 7= 6.3 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.37, 155.04, 144.43, 142.16, 132.90 (d,7= 2.7 Hz), 131.93, 131.87, 130.51, 130.46, 128.13, 127.70, 125.08, 124.99, 80.20, 78.55, 74.10, 49.16, 34.67, 28.25, 14.28
34 ... ... ESIMS m/z 486.5 ([M-H2O]+) 1H NMR (400 MHz, CDC13) δ 7.37 7.28 (m, 4H), 7.18 (ddd, 7= 8.4, 2.2, 0.8 Hz, 1H), 7.09 (ddd, 7= 8.4, 2.2, 0.9 Hz, 1H), 5.86 (q, 7= 6.2 Hz, 1H), 4.93 (d, 7= 7.8 Hz, 1H), 4.14 (t, 7= 7.4 Hz, 1H), 3.06 (s, 1H), 1.41 (s,9H), 1.18 (d, 7 =6.3 Hz, 3H), 0.98 (d, 7= 6.8 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.28, 158.09 (d, 7= 249.9 Hz), 158.06 (d, 7= 249.5 Hz), 155.05, 145.31 (d,7=5.7 Hz), 142.98, 130.64 (d,7= 10.0 Hz), 121.90 (d, 7= 8.8 Hz), 120.38 (d, 7= 12.3 Hz), 120.24 (d,7= 12.3 Hz), 114.59 (d, 7= 22.6 Hz), 114.20 (d, 7= 22.9 Hz), 80.19, 78.60, 74.13, 49.13, 34.67, 28.25, 14.30
210
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
35 ... ... ESIMS m/z 480.6 ([M]+) 1H NMR (400 MHz, CDC13) δ 7.24 (dd, J = 10.4, 8.1 Hz, 2H), 7.09 (dd, J= 5.5, 2.2 Hz, 2H), 7.02 (td, J= 8.6, 2.3 Hz, 2H), 5.69 (dq, 7= 10.1, 6.1 Hz, 1H), 4.94 (d,7 = 7.9 Hz, 1H), 4.13 (t, 7= 7.5 Hz, 1H), 3.92 (d, 7= 10.0 Hz, 1H), 2.33 (s, 3H), 2.31 (s, 3H), 1.42 (s, 9H), 1.21 (d, 7 =6.1 Hz, 3H), 0.84 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.81, 154.92, 139.66, 139.44, 136.53, 136.10, 133.08, 132.72, 130.69, 130.57, 129.43, 129.12, 126.59, 126.46, 79.77, 72.61, 56.49, 49.17, 28.29, 20.16, 20.09, 19.23, 18.09
36 ... (Thin film) 3385, 2980, 1669, 1486, 1452, 1160,757 — 'H NMR (300 MHz, CDC13) δ 7.82 (ddd, 7=8.6, 7.3, 1.8 Hz, 1H), 7.51 (tt,7=7.9, 1.5 Hz, 1H), 7.33 - 7.12 (m, 3H), 7.09 (td, 7= 7.6, 1.4 Hz, 1H), 6.94 (dd, 7= 8.1, 1.4 Hz, 1H), 6.90 (dd,7=8.1, 1.4 Hz, 1H), 6.23 (qd,7=6.3, 1.6 Hz, 1H), 5.02 (d, 7= 7.9 Hz, 1H), 4.30 - 4.13 (m, 1H), 3.21 (s, 1H), 1.42 (s, 9H), 1.26 (d,7 = 6.2 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H)
37 ... (Thin film) 3375, 2981, 1703, 1609, 1515, 1453, 1433, 1380, 1367, 1284, 1250, 1208, 1162, 1113, 1053, 1023, 967, 909,873, 821, 754, 731 HRMS-ESI (m/z) [M+Na]+ calcd for C23H25F4NNaO4, 478.1612; found, 478.1624 'H NMR (300 MHz, CDC13) δ 7.18 6.91 (m, 6H), 5.63 (dq, 7= 9.4, 6.2 Hz, 1H), 4.92 (d, 7= 8.0 Hz, 1H), 4.24 - 4.06 (m, 1H), 3.98 (d, 7= 9.5 Hz, 1H), 1.42 (s, 9H), 1.23 (d,7=6.1Hz, 3H), 0.91 (d, 7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -136.25 (dt,7=20.6, 9.7 Hz), -136.69 (dt,7=20.4, 9.9 Hz), -139.30 (dd, 7= 21.3, 10.5 Hz), -139.70 (dd,7= 21.1, 10.1 Hz)
211
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
38 ... (Thin film) 3440, 2981, 1704, 1600, 1497, 1452, 1379, 1367, 1306, 1250, 1210, 1162, 1095, 1054, 1023, 907, 867, 822, 799, 780, 731,719, 689 HRMS-ESI (m/z) [M+Na]+ calcd for C23H25Cl2F2NNaO4, 510.1021; found, 510.1033 1H NMR (300 MHz, CDC13) δ 7.32 7.22 (m, 2H), 7.18 - 7.02 (m, 4H), 5.64 (dq, J= 9.6, 6.2 Hz, 1H), 4.93 (d, J= 8.0 Hz, 1H), 4.25 - 4.03 (m, 1H), 3.98 (d, J= 9.6 Hz, 1H), 1.42 (s, 9H), 1.23 (d, J =6.2 Hz, 3H), 0.92 (d, J= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -116.98 (q, J= 6.9 Hz), -117.44 (q, J= 6.8 Hz)
39 ... (Thin film) 3364, 2980, 2931, 1707, 1597, 1501, 1451, 1379, 1366, 1307, 1248, 1207, 1163, 1118, 1052, 1023, 959, 908, 881, 821,781, 731 HRMS-ESI (m/z) [M+Na]+ calcd for C25H3 iF2NNaO4, 470.2113; found, 470.2120 ΉΝΜΚ(300 MHz, CDC13) 5 7.13 6.98 (m, 4H), 6.90 (td, J= 9.1, 7.4 Hz, 2H), 5.67 (dq, J= 10.1, 6.1 Hz, 1H), 4.93 (d, J= 8.0 Hz, 1H), 4.22 - 4.02 (m, 1H), 3.91 (d,7= 10.1 Hz, 1H), 2.23 (d, 7=2.0 Hz, 3H), 2.21 (d, 7= 2.0 Hz, 3H), 1.42 (s, 9H), 1.21 (d, 7= 6.1 Hz, 3H), 0.83 (d,7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -119.99 (q, 7= 6.8 Hz), -120.57 (q, 7= 7.0 Hz)
212
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
40 — — ESIMS m/z 536 ([M+H]+) 'H NMR (400 MHz, CDC13) δ 7.53 (ddd, J= 13.6, 6.7, 4.2 Hz, 8H), 7.45 - 7.37 (m, 8H), 7.35 - 7.29 (m, 2H), 5.87 (dq, J = 12.3, 6.1 Hz, 1H), 4.94 (d,7= 7.1 Hz, 1H), 4.18- 4.09 (m, 2H), 1.41 (s, 9H), 1.31 (d, 7= 6.2 Hz, 3H), 0.80 (d,7=7.1 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.93, 154.96, 140.72, 140.60, 140.56, 140.21, 139.92, 139.68, 128.76, 128.75, 128.51, 127.58, 127.30, 127.27, 127.23, 127.00, 126.96, 79.70, 73.12, 57.33, 49.22, 28.31, 19.39, 18.04
43 — — HRMS-ESI (m/z) [M+Na]+ calcd for C23H25Cl4NNaO4, 542.0430; found, 542.0442 1H NMR (400 MHz, CDC13) δ 7.38 (t, 7 = 8.1 Hz, 2H), 7.32 (dd,7= 13.6, 2.1 Hz, 2H), 7.10 (dd,7= 8.4, 2.1 Hz, 1H), 7.07 (dd,7= 8.4, 2.1 Hz, 1H), 5.65 (dq,7= 9.5, 6.2 Hz, 1H), 4.93 (d,7= 7.9 Hz, 1H), 4.22 - 4.09 (m, 1H), 3.97 (d, 7= 9.5 Hz, 1H), 1.42 (d, 7= 0.9 Hz, 9H), 1.24 (d, 7= 6.1 Hz, 3H), 0.93 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.73, 154.93, 140.37, 140.26, 133.10, 132.76, 131.66, 131.34, 130.97, 130.67, 130.23, 130.06, 127.34, 127.27, 79.92, 71.96, 55.79, 49.16, 28.29, 19.14, 18.11
213
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
44 ... ... HRMS-ESI (m/z) [M+Na]+ calcd for C23H25Cl2F2NNaO4, 510.1021; found, 510.1030 'H NMR (400 MHz, CDC13) δ 7.38 7.28 (m, 2H), 7.06 (dd, J= 10.0, 1.8 Hz, 1H), 7.04 - 6.94 (m, 3H), 5.66 (ddt, J= 9.1, 6.9, 5.5 Hz, 1H), 4.92 (d, J= 8.0 Hz, 1H), 4.22 - 4.08 (m, 1H), 4.01 (d, J= 9.4 Hz, 1H), 1.42 (d,7= 1.3 Hz, 9H), 1.24 (dd,7= 6.2, 1.3 Hz, 3H), 0.92 (d,7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.68, 158.17 (d, 7= 250.1 Hz), 158.03 (d, 7= 250.1 Hz), 154.93, 141.08 (d,7=6.1 Hz), 140.95 (d,7=6.1 Hz), 131.11, 130.80, 124.51 (d, 7= 3.3 Hz), 124.36 (d, 7= 3.6 Hz), 120.08 (d,7= 17.6 Hz), 119.78 (d, 7= 17.6 Hz), 116.48 (d, 7= 16.8 Hz), 116.24, 79.92, 72.02, 56.07, 49.15,28.28, 19.10, 18.10
45 ... ... ESIMS m/z 300 ([M+H]+) ...
46 ... ... ESIMS m/z 284.3 ([M+H]+) ...
47 ... ... ESIMS m/z 296.3 ([M+H]+) ...
214
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
48 ... (Thin film) 3395, 2885, 1741, 1603, 1508, 1459, 1381, 1324, 1224, 1159, 1137, 1118, 1049, 1015,955, 881,826, 793, 779, 755, 746, 721, 693, 666 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H20F2NO2, 320.1457; found, 320.1457 'H NMR (400 MHz, CDC13) δ 8.55 (s, 3H), 7.22 (dt, J= 9.0, 4.8 Hz, 4H), 6.98 (q, J= 8.2 Hz, 4H), 5.71 (dq,7= 11.8, 6.1Hz, 1H), 4.05 (d,7= 9.8 Hz, 2H), 1.23 (d, 7= 5.9 Hz, 3H), 1.13 (d,7=6.7 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -115.32,-115.70
49 ... ... ESIMS m/z 341.5 ([M+Na]+) ...
50 ... ... ESIMS m/z 314.6 ([M+H]+) ...
51 ... ... ESIMS m/z 356.4 ([M+H]+) ...
52 ... ... ESIMS m/z 302.4 ([M+H]+) 19F NMR (376 MHz, CDC13) δ -169.31
53 ... ... ESIMS m/z 344.5 ([M+H]+) ...
215
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
54 ... ... ESIMS m/z 320.4 ([M+H]+) ...
55 ... ... ESIMS m/z 352.4 ([M+H]+) ...
56 ... ... ESIMS m/z 282.4 ([M+H]+) ...
57 ... ... ESIMS m/z 298.4 ([M+H]+) ...
58 ... ... ESIMS m/z 442.4 ([M+H]+) ...
59 ... ... ESIMS m/z 324.4 ([M+H]+) ...
60 ... ... ESIMS m/z 312.3 ([M+H]+) ...
61 ... ... ESIMS m/z 436 ([M+H]+) ...
63 ... ... ESIMS m/z 375.5 ([M+Na]+) ...
64 ... ... ESIMS m/z 375.5 ([M+Na]+) ...
216
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
65 ... ... ESIMS m/z 344.5 ([M+H]+) ...
66 ... ... ESIMS m/z 344.5 ([M+H]+) ...
67 ... ... ESIMS m/z 348.5 ([M+H]+) ...
68 ... ... ESIMS m/z 380.5 ([M+H]+) ...
69 ... ... ESIMS m/z 332.5 ([M+H]+) ...
70 ... ... ESIMS m/z 340.5 ([M+H]+) ...
71 ... (Thin film) 2959, 1749, 1508, 1401, 1229, 1159, 1055, 830 HRMS-ESI (m/z) ([M+H]+) calcd calcd for c17h17f2no2, 306.1300; found, 306.1298 ...
217
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¥, 13C, 19F)
72 ... (Thin film) 3452, 2855, 1742, 1601, 1506, 1454, 1220, 1159, 1136, 1046, 824 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C19H22F2NO2, 335.1646; found, 335.1646 ...
73 ... (Thin film) 2966, 1736, 1602, 1507, 1221, 1158, 1120, 1046, 825 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C20H24F2NO2, 349.1803; found, 349.1804 ...
74 ... (Thin film) 2959, 1739, 1603, 1507, 1219, 1158, 1132, 1046, 825 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C21H26F2NO2, 363.1959; found, 363.1959 ...
75 ... (Thin film) 3411, 2986, 1740, 1605, 1509, 1453, 1223, 1137, 1116, 1049, 700 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H21FNO2, 302.1551; found, 302.1551 ...
218
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
77 ... (Thin film) 3363, 2941, 1743, 1467, 1385, 1236, 1201, 1173, 1136, 1117, 1061, 1029, 992, 824,755, 723, 675 ESIMS m/z 438.0 ([M+H]+) ...
78 ... (Thin film) 3361, 2942, 1742, 1582, 1486, 1419, 1240, 1207, 1141, 1116, 1057, 800 ESIMS m/z 404.0 ([M]+) ...
79 ... (Thin film) 3218, 2980, 2945, 1742, 1522, 1481, 1245, 1216, 1136, 1118, 1048,758 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C20H24CI2NO2, 380.1179; found, 380.1181 ...
219
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
80 ... ... ESIMS m/z 404.4 ([M+H]+) ...
81 ... ... ESIMS m/z 336.5 ([M+H]+) ...
83 ... ... ESIMS m/z 408.5 ([M+H]+) ...
84 ... (Thin film) 2881, 2193, 2130, 1742, 1609, 1516, 1457, 1434, 1383, 1325, 1285, 1208, 1118, 1049, 966, 906,875, 821, 754, 710, 692, 681,656 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H18F4NO2, 356.1268; found, 356.1273 1H NMR (300 MHz, mcthanol-0/4) δ 7.46 - 7.30 (m, 2H), 7.28 - 7.14 (m, 4H), 5.84 (dq, 7= 10.1, 6.2 Hz, 1H), 4.24 (d, 7= 10.1 Hz, 1H), 3.96 (q,7=7.3Hz, 1H), 3.31 (pd, 7= 1.6, 0.5 Hz, 3H), 1.27 (d,7 = 6.1 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H) 19F NMR (471 MHz, methanol-74) δ 139.39 (ddd, 7= 19.8, 11.5, 7.5 Hz), -139.57 - -139.84 (m), -142.33 -142.56 (m), -142.66 - -142.93 (m)
220
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
85 ... (Thin film) 3409, 2928, 2026, 1957, 1743, 1597, 1499, 1458, 1408, 1323, 1249, 1208, 1118, 1061,917, 866, 822, 798, 780, 753,718, 690, 663 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H18C12F2NO2, 388.0677; found, 388.0677 1H NMR (300 MHz, methanol-/) δ 7.54 (dt, J= 7.0, 2.7 Hz, 2H), 7.37 (ddt, J= 8.6, 4.3, 2.1 Hz, 2H), 7.21 (td, J= 8.8, 4.7 Hz, 2H), 5.93 - 5.75 (m, 1H), 4.24 (d, J= 10.1 Hz, 1H), 3.96 (q, J= 7.3 Hz, 1H), 3.31 (t,7= 1.7 Hz, 3H), 1.28 (d,7= 6.1Hz, 3H), 1.03 (d, 7= 7.3 Hz, 3H) 19F NMR (471 MHz, methanol-/) δ -119.62--119.72 (m),-119.99-120.08 (m)
86 ... (Thin film) 3374, 2928, 1742, 1596, 1501, 1457, 1379, 1323, 1233, 1206, 1118, 1052, 1003, 956, 933, 886, 824, 780, 752, 721, 711,690, 681,671, 664, 655 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C2oH24F2N02, 348.1770; found, 348.1771 1H NMR (300 MHz, methanol-/) δ 7.30 - 7.12 (m, 4H), 6.95 (td, 7= 8.9, 6.6 Hz, 2H), 5.91-5.74 (m, 1H), 4.07 (d,7= 10.4 Hz, 1H), 3.99 - 3.83 (m, 1H), 3.30 (dtd, 7= 3.3, 1.6, 0.6 Hz, 3H), 2.23 (t,7= 2.6 Hz, 6H), 1.25 (d,7=6.1Hz, 3H), 0.94 (dd,7=7.3, 0.7 Hz, 3H) 19F NMR (471 MHz, methanol-/) δ -122.00 - -122.37 (m), -122.69 (tt, 7= 6.1,2.9 Hz)
221
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
87 ... (Thin film) 2879, 1746, 1587, 1561, 1517, 1468, 1395, 1227, 1194, 1116, 1053, 1029, 871, 822, 747, 727, 669 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H18CI4NO2, 420.0086; found, 420.0090 ...
88 ... (Thin film) 2858, 1747, 1580, 1486, 1458, 1383, 1368, 1278, 1236, 1206, 1119, 1048, 970, 871, 824, 779, 761, 682 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C18H18CI2F2NO2, 388.0677; found, 388.0688 ...
222
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
89 ... ... HRMS-ESI (m/z) [M]+ calcd for C25H26N2O6, 450.1791; found, 450.1794 Ή NMR (500 MHz, CDC13) δ 11.97 (d, J = 0.5 Hz, 1H), 8.33 (d, J= 8.1 Hz, 1H), 7.96 (d, J= 5.2 Hz, 1H), 7.47 (ddt, J= 8.5, 6.4, 1.3 Hz, 4H), 7.33 - 7.13 (m, 5H), 6.89 - 6.81 (m, 1H), 6.03 (q, J= 6.3 Hz, 1H), 4.62 - 4.49 (m, 1H), 3.93 (s, 3H), 2.74 (s, 1H), 1.23 (d, J= 6.3 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.30, 168.61, 155.37, 148.71, 144.85, 142.71, 140.44, 130.29, 128.33, 128.32, 127.22, 127.16, 125.51, 125.45, 109.44, 79.57, 75.54, 56.08, 47.85, 17.62, 14.32
90 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H27N2O5, 435.1920; found, 435.1925 1H NMR (400 MHz, CDC13) δ 12.10 (d, J = 0.6 Hz, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.38 - 7.06 (m, 10H), 6.86 (dd, J= 5.3, 0.7 Hz, 1H), 5.83 (dq,7= 10.1, 6.1 Hz, 1H), 4.52 (dq,7= 8.1,7.2 Hz, 1H), 4.06 (d, 7= 10.2 Hz, 1H), 3.93 (s, 3H), 1.26 (d,7=6.1 Hz, 3H), 0.97 (d,7=7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.67, 168.53, 155.34, 148.72, 141.38, 141.13, 140.40, 130.48, 128.80, 128.50, 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93,56.07, 47.85, 19.24, 17.61
91 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C21H23N2O5S2, 447.1048; found, 447.1047 1H NMR (400 MHz, CDC13) δ 12.10 (d, 7 = 0.6 Hz, 1H), 8.41 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.18 - 7.16 (m, 2H), 7.01 (ddd, 7=3.6, 1.3,0.6 Hz, 1H), 6.94 - 6.88 (m, 3H), 6.86 (dd, 7= 5.3, 0.7 Hz, 1H), 5.56 (dq, 7= 7.4, 6.2 Hz, 1H), 4.70 - 4.58 (m, 2H), 3.94 (s, 3H), 1.30 (d, 7= 6.2 Hz, 3H), 1.24 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.48, 168.62, 155.35, 148.74, 143.75, 142.69, 140.43, 130.48, 126.77, 126.57, 126.05, 125.43, 124.61, 124.58, 109.44, 74.83, 56.08,47.98, 47.42, 18.69, 17.80
223
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
92 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25F2N2O5, 471.1731; found, 471.1735 Ή NMR (400 MHz, CDC13) δ 12.06 (d, J = 0.7 Hz, 1H), 8.32 (d, J= 8.0 Hz, 1H), 7.98 (d, 7= 5.3 Hz, 1H), 7.26 - 7.18 (m, 4H), 7.01 - 6.89 (m, 4H), 6.87 (d, J= 5.3 Hz, 1H),5.73 (dq, 7= 9.7,6.1 Hz, 1H), 4.59 _ 4.49 (m, 1H), 4.05 (d, J= 9.8 Hz, 1H), 3.94 (s, 3H), 1.25 (d, J= 6.2 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -115.46,-115.80
93 ... ... HRMS-ESI (m/z) [2M+Na]+ calcd for C54H6oN4NaO 12, 979.4106; found, 979.4119 'H NMR (400 MHz, CDC13) δ 12.03 (d,7 = 0.7 Hz, 1H), 8.40 (d, 7= 8.1 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.41 - 7.09 (m, 10H), 6.85 (d,7= 5.2 Hz, 1H), 5.97 (q,7 = 6.3 Hz, 1H), 4.61 (dq, 7= 8.2, 7.2 Hz, 1H), 3.94 (s, 3H), 3.39 (dq, 7= 9.1, 6.9 Hz, 1H), 3.18 (dq, 7= 9.2, 6.9 Hz, 1H), 1.30 (d, 7= 7.2 Hz, 3H), 1.17 (t, 7= 6.9 Hz, 3H), 1.13 (d, 7= 6.3 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.45, 168.56, 155.34, 148.71, 141.84, 140.56, 140.38, 130.37, 128.25, 127.87, 127.81, 127.69, 127.33, 127.21, 109.41, 84.05, 74.30, 59.93, 56.08, 48.05, 18.02, 15.67, 14.95
95 ... ... HRMS-ESI (m/z) [M-0CH3]+ calcd for C25H25N2O5, 433.1764; found, 433.1763 1H NMR (300 MHz, CDC13) δ 12.04 (d, J = 0.6 Hz, 1H), 8.41 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.41 - 7.18 (m, 10H), 6.85 (d,7= 5.4 Hz, 1H), 5.97 (q,7 = 6.3 Hz, 1H), 4.75 - 4.49 (m, 1H), 3.94 (s, 3H),3.15(s, 3H), 1.29 (d, 7= 7.2 Hz, 3H), 1.13 (d, 7= 6.3 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.42, 168.58, 155.35, 148.72, 141.11, 140.39, 139.89, 130.37, 128.51, 128.11, 127.86, 127.69, 127.52, 127.31, 109.42, 84.47, 74.02, 56.08, 52.55, 48.05, 17.97, 14.97
224
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
96 ... ... ... 'H NMR (400 MHz, CDC13) δ 12.03 (d, J = 0.6 Hz, 1H), 8.31 (d, J= 7.9 Hz, 1H), 7.97 (d, J= 5.2 Hz, 1H), 7.35 (td, J= 8.5, 6.2 Hz, 1H), 7.23 (td, J= 8.4, 6.2 Hz, 1H), 6.91 - 6.74 (m, 4H), 6.69 (ddd, J= 10.4, 8.8, 2.6 Hz, 1H), 5.88 - 5.74 (m, 1H), 4.69 (d, J= 9.9 Hz, 1H), 4.64 - 4.48 (m, 1H), 3.95 (s, 3H), 1.30 (d,7= 6.1 Hz, 3H), 1.17 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -110.97 (d, 7= 7.7 Hz), -111.39 (d, 7= 7.6 Hz), -111.98 (dd, 7= 7.7, 2.6 Hz), 112.83 (dd, 7= 7.6, 2.6 Hz)
97 ... ... ... 'H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.31 (d, 7= 7.9 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.49 - 7.40 (m, 4H), 7.37 7.24 (m, 5H), 7.23 - 7.18 (m, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.00 (dq, 7= 25.4, 6.4 Hz, 1H), 4.63 - 4.51 (m, 1H), 3.94 (s, 3H), 1.32 (dd,7=6.5, 1.0 Hz, 3H), 0.96 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -169.17
98 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C27H31N2O7, 495.2131; found, 495.2124 'H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.22 - 7.12 (m, 4H), 6.90 6.73 (m, 5H), 5.73 (dq,7= 9.8, 6.1 Hz, 1H), 4.64 - 4.44 (m, 1H), 3.96 (d, 7= 9.9 Hz, 1H), 3 .93 (s, 3H), 3.75 (s, 3H), 3.73 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.05 (d, 7=7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.65, 168.54, 158.36, 158.20, 155.34, 148.70, 140.40, 133.83, 133.69, 130.45, 128.97, 128.92, 114.11, 113.81, 109.39, 73.77, 56.11, 56.04, 55.20, 55.19, 47.90, 19.20, 17.75
225
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
99 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25F2N2O5, 471.1731; found, 471.1724 'H NMR (400 MHz, CDCh) δ 12.05 (s, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.3 Hz, 1H), 7.32-7.19 (m, 2H),7.117.03 (m, 2H), 7.02 - 6.83 (m, 5H), 5.75 (dq, J= 9.8, 6.1Hz, 1H), 4.65 - 4.46 (m, 1H), 4.06 (d, J= 9.9 Hz, 1H), 3.94 (s, 3H), 1.27 (d, ./= 6.1 Hz, 3H), 1.07 (d,J= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCh) δ -112.07,-112.48
100 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25CI2N2O5, 503.1140; found, 503.1137 'H NMR (400 MHz, CDCh) δ 12.04 (s, 1H), 8.32 (d, J= 7.7 Hz, 1H), 7.98 (d, J= 5.3 Hz, 1H), 7.31 - 7.10 (m, 8H), 6.86 (d, J= 5.2 Hz, 1H), 5.73 (dq, J= 9.9, 6.2 Hz, 1H), 4.60 - 4.48 (m, 1H), 4.01 (d, J= 10.0 Hz, 1H), 3.94 (s, 3H), 1.27 (d, J= 6.2 Hz, 3H), 1.08 (d,J=7.1Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.55, 168.60, 155.36, 148.72, 142.54, 142.33, 140.47, 134.73, 134.42, 130.33, 130.23, 129.94, 128.42, 128.33, 127.52, 127.21, 126.18, 125.98, 109.47, 72.83, 57.03, 56.08,47.85, 19.11, 17.66
101 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25N2O5, 433.1763; found, 433.1749 'H NMR (400 MHz, CDCh) δ 12.23 11.94 (m, 1H), 8.64-8.39 (m, 1H), 8.11 - 7.92 (m, 1H), 7.78 - 7.60 (m, 3H), 7.59 - 7.48 (m, 1H), 7.46 - 7.35 (m, 2H), 7.36 - 7.26 (m, 1H), 7.27 - 7.20 (m, 1H), 6.91 - 6.84 (m, 1H), 5.87 - 5.69 (m, 1H), 4.94 - 4.76 (m, 1H), 4.35 - 4.22 (m, 1H), 4.00 -3.93(m, 3H), 1.69- 1.51 (m, 3H), 0.95 - 0.59 (m, 3H)
102 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25N2O6, 449.1712; found, 449.1707 'H NMR (400 MHz, CDCh) δ 12.16 (s, 1H), 8.51 -8.38 (m, 1H), 8.11 - 7.82 (m, 1H), 7.34 - 7.15 (m, 4H), 7.15- 6.94 (m, 4H), 6.91 - 6.77 (m, 1H), 5.20 - 5.09 (m, 1H), 4.78 - 4.64 (m, 1H), 4.33-4.17 (m, 1H), 3.96 - 9.92 (m, 3H), 1.55 - 1.42 (m, 3H), 1.10-0.91 (m, 3H)
226
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
103 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25Br2N2O5, 591.0130; found, 591.0125 'H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.33 (d, J= 7.9 Hz, 1H), 7.97 (d, J= 5.2 Hz, 1H), 7.50 - 7.31 (m, 4H), 7.24 7.01 (m, 4H), 6.87 (d, J= 5.2 Hz, 1H), 5.73 (dq,/=9.6, 6.1Hz, 1H), 4.55 (p,/ = 7.3 Hz, 1H), 4.01 (d, J= 9.7 Hz, 1H), 3.93 (s, 3H), 1.25 (d,/= 6.1 Hz, 3H), 1.09 (d,/= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.50, 168.61, 155.39, 148.74, 140.47, 139.69, 139.59, 132.00, 131.69, 130.31, 129.80, 129.73, 121.12, 120.84, 109.52, 72.81, 56.45, 56.08, 47.86, 19.09, 17.67
104 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C23H27N2O5S2, 475.1361; found, 475.1368 'Η NMR(400 MHz, CDC13) δ 12.13 (s, 1H), 8.44 (d, /= 8.0 Hz, 1H), 7.99 (d, /= 5.2 Hz, 1H), 6.87 (d, /= 5.2 Hz, 1H), 6.73 (d, /= 3.4 Hz, 1H), 6.67 (d, /= 3.4 Hz, 1H), 6.54 - 6.35 (m, 2H), 5.54 - 5.40 (m, 1H), 4.78 - 4.59 (m, 1H), 4.45 (d, /= 7.1 Hz, 1H), 3.94 (s, 3H), 2.39 (s, 6H), 1.30 (d,/= 2.8 Hz, 3H), 1.28 (d,/= 3.7 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.50, 168.60, 155.35, 148.74, 141.52, 140.47, 140.41, 139.03, 139.00, 130.53, 125.76, 125.08, 124.67, 124.42, 109.41, 74.68, 56.07, 48.00, 47.84, 18.65, 17.88, 15.25
105 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C27H31N2O5, 463.2233; found, 463.2242 'Η NMR(400 MHz, CDC13) δ 12.14 (s, 1H), 8.38 (d, /= 8.0 Hz, 1H), 7.94 (d, /= 5.2 Hz, 1H), 7.21 - 7.10 (m, 4H), 7.09 6.97 (m, 4H), 6.82 (d, /= 5.2 Hz, 1H), 5.79 (dq, /= 10.1, 6.2 Hz, 1H), 4.53 (p, J = 7.3 Hz, 1H), 3.98 (d, /= 10.0 Hz, 1H), 3.88 (s, 3H), 2.25 (s, 3H), 2.23 (s, 3H), 1.25 (d,/= 6.3 Hz, 3H), 1.01 (d,/= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.66, 168.57, 155.32, 148.71, 140.43, 138.63, 138.47, 136.37, 136.05, 130.45, 129.44, 129.11, 127.91, 127.85, 109.45, 73.66, 57.08, 56.02, 47.92, 20.97, 20.93, 19.24, 17.64
227
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (A 13c, 19f)
106 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C26H26F3N2O5, 503.1794; found, 503.1794 'H NMR (400 MHz, CDCfi) δ 12.09 (s, 1H), 8.35 (d, J= 8.0 Hz, 1H), 7.97 (d, J= 5.2 Hz, 1H), 7.54 (d, J= 8.1 Hz, 2H), 7.42 (d,7=8.1Hz, 2H), 7.34 -7.21 (m, 4H), 7.21-7.13 (m, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 5.85 (dq, 7= 9.8, 6.1 Hz, 1H), 4.61-4.46 (m, 1H),4.15 (d, 7= 9.9 Hz, 1H), 3.93 (s, 3H), 1.27 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCfi) δ -62.53
107 ... ... HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H25CI2N2O5, 503.1140; found, 503.1139 'H NMR (400 MHz, CDCfi) δ 12.05 (s, 1H), 8.32 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.38-7.10 (m, 8H), 6.87 (d, 7= 5.2 Hz, 1H), 5.73 (dq, 7= 9.9, 6.2 Hz, 1H), 4.62 - 4.45 (m, 1H), 4.03 (d, 7= 9.6 Hz, 1H), 3.94 (s, 3H), 1.25 (d, 7 = 6.1 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDCfi) δ 171.52, 168.61, 155.41, 148.74, 140.45, 139.26, 139.15, 133.04, 132.77, 130.32, 129.41, 129.36, 129.05, 128.73, 109.49, 72.95, 56.35,56.08, 47.86, 19.08, 17.67
109 ... ... ESIMS m/z 587 ([M+H]+) 'H NMR (400 MHz, CDCfi) δ 12.10 (s, 1H), 8.36 (d, 7= 7.9 Hz, 1H), 7.95 (d, 7= 5.2 Hz, 1H), 7.57 - 7.46 (m, 8H), 7.43 7.38 (m, 7H), 7.34 - 7.29 (m, 2H), 6.81 (d, 7= 5.2 Hz, 1H), 5.90 (dq, 7= 12.2, 6.1 Hz, 1H), 4.56 (p, 7= 7.2 Hz, 1H), 4.16 (d, 7= 10.0 Hz, 1H), 3.89 (d,7= 1.9 Hz, 3H), 1.34 (d, 7= 6.1 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDCfi) δ 171.71, 168.59, 155.33, 148.72, 140.65, 140.58, 140.43, 140.11, 139.94, 139.66, 130.44, 128.77, 128.73, 128.67, 128.53, 127.58, 127.30, 127.26, 127.21, 127.00, 126.94, 109.40, 73.58, 57.25, 56.04, 47.91, 19.33, 17.66
228
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
110 — (Thin film) 3374, 2984, 1735, 1649, 1602, 1577, 1530, 1507, 1449, 1380, 1329, 1296, 1222, 1188, 1159, 1130, 1105, 1049, 1015,906, 826, 809, 792, 778, 731,704, 666 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C24H23F2N2O4, 441.1620; found, 441.1620 1H NMR (400 MHz, CDCfi) δ 11.80 (s, 1H), 8.30 (d, J= 8.0 Hz, 1H), 8.07 (dd, J = 4.3, 1.5 Hz, 1H), 7.40-7.15 (m, 6H), 7.05 - 6.85 (m, 4H), 5.73 (dq, J= 9.8, 6.2 Hz, 1H), 4.65 - 4.45 (m, 1H), 4.05 (d, J= 9.8 Hz, 1H), 1.25 (d, 7= 6.1 Hz, 3H), 1.07 (d,7=7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.60, 168.26, 161.76 (d, 7= 246.1 Hz), 161.64 (d, 7 = 245.7 Hz), 157.79, 139.65, 136.82 (d, 7= 3.3 Hz), 136.71 (d, 7= 3.5 Hz), 131.04, 129.50 (d, 7= 7.9 Hz), 128.80, 126.08, 115.74 (d,7=21.3 Hz), 115.41 (d, 7= 21.3 Hz), 73.34, 56.14, 47.84, 19.12, 17.69 19F NMR (376 MHz, CDC13) δ -115.44,-115.76
229
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
Ill — (Thin film) 3370, 2984, 2936, 2256, 1735, 1647, 1604, 1574, 1529, 1507, 1483, 1469, 1452, 1381, 1323, 1281, 1262, 1222, 1158, 1109, 1048, 1015,990, 904, 824, 800, 730 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C26H27F2N2O5, 485.1883; found, 485.1880 Ή NMR (400 MHz, CDC13) δ 12.06 (d, J = 0.6 Hz, 1H), 8.33 (d, J= 8.0 Hz, 1H), 7.95 (d, 7= 5.2 Hz, 1H), 7.35 - 7.14 (m, 4H), 7.04 - 6.87 (m, 4H), 6.84 (d, 7= 5.2 Hz, 1H), 5.73 (dq, 7= 9.7,6.1 Hz, 1H), 4.60-4.48 (m, 1H), 4.16 (q, 7= 7.0 Hz, 2H), 4.05 (d, 7= 9.7 Hz, 1H), 1.51 (t, 7= 7.0 Hz, 3H), 1.24 (d,7=6.1Hz, 3H), 1.06 (d,7=7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.58, 168.66, 161.75 (d, 7= 246.1 Hz), 161.64 (d, 7 = 245.7 Hz), 154.75, 148.82, 140.38, 136.82 (d, 7= 3.3 Hz), 136.73 (d, 7=3.3 Hz), 130.41, 129.51 (d,7=7.6 Hz), 115.72 (d, 7= 21.4 Hz), 115.39 (d, 7 = 21.2 Hz), 110.13, 73.32, 64.67, 56.12, 47.84, 19.11, 17.69, 14.37 19F NMR (376 MHz, CDC13) δ -115.47,-115.80
230
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¥, 13C, 19F)
112 ... (Thin film) 3370, 2984, 1729, 1641, 1601, 1531, 1507, 1491, 1450, 1361, 1305, 1281, 1254, 1222, 1177, 1158, 1135, 1087, 1048, 1015,908, 824, 778, 752, 731, 666 HRMS-ESI (m/z) ([M+H]+) calcd calcd for C25H24F2NO4, 440.1668; found, 440.1676 'H NMR (400 MHz, CDC13) δ 12.05 (s, 1H), 7.43 - 7.33 (m, 2H), 7.30 - 7.17 (m, 4H), 7.05 - 6.90 (m, 5H), 6.88 - 6.77 (m, 2H), 5.75 (dq, 7=9.9, 6.1Hz, 1H), 4.57 (p, 7 =7.1 Hz, 1H), 4.06 (d, 7= 9.9 Hz, 1H), 1.25 (d, 7= 6.1 Hz, 3H), 1.00 (d,7= 7.1Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.22, 169.33, 161.79 (d, 7= 246.2 Hz), 161.70 (d,7 = 245.9 Hz), 161.59, 136.83 (d,7= 3.4 Hz), 136.61 (d, 7= 3.4 Hz), 134.49, 129.49 (d, 7= 8.1 Hz), 129.46 (d, 7= 7.9 Hz), 125.62, 118.70, 118.58, 115.79 (d, 7 = 21.4 Hz), 115.50 (d, 7= 21.3 Hz), 113.72, 73.62, 56.17, 48.29, 19.15, 17.79 19F NMR (376 MHz, CDC13) δ -115.30,-115.60
113 ... ... ESIMS m/z 457.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 11.98 (d, 7 = 0.6 Hz, 1H), 8.30 (t, 7= 5.7 Hz, 1H), 7.99 (d, 7= 5.2 Hz, 1H), 7.24 - 7.15 (m, 4H), 7.03 - 6.85 (m, 5H), 5.71 (dq, 7= 9.2, 6.2 Hz, 1H), 4.11 (dd,7= 18.1,6.0 Hz, 1H), 4.04 (d, 7= 9.2 Hz, 1H), 3.95 (s, 3H), 3.90 (dd, 7= 18.1, 5.6 Hz, 1H), 1.25 (d, 7= 6.3 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 169.18, 168.43, 161.74 (d, 7= 246.1 Hz), 161.63 (d, 7= 245.5 Hz), 155.42, 148.71, 140.55, 136.68, 130.30, 129.68, 129.60, 115.67 (d, 7= 29.2 Hz), 115.46 (d, 7= 29.1 Hz), 109.55, 73.65, 56.11, 55.77, 40.91, 19.12
231
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
114 ... ... ESIMS m/z 485.6 ([M+H]+) 'H NMR (400 MHz, CDC13) δ 12.08 (s, 1H), 8.32 (d, J= 8.5 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.46 - 7.04 (m, 4H), 7.116.65 (m, 5H), 5.71 (dq, J= 9.8, 6.2 Hz, 1H), 4.51 (ddd,7=8.5, 7.0,5.4 Hz, 1H), 4.05 (d, J= 9.6 Hz, 1H), 3.95 (s, 3H), 1.70- 1.57 (m, 1H), 1.49- 1.36 (m, 1H), 1.24 (d, J= 6.2 Hz, 3H), 0.67 (t, J= 7.5 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 170.87, 168.79, 161.74 (d, J= 245.9 Hz), 161.66 (d, J= 245.8 Hz), 155.43, 148.73, 140.42, 136.80, 130.36, 129.55 (d, 7= 2.7 Hz), 129.47 (d, J= 2.7 Hz), 115.67 (d, J= 32.4 Hz), 115.45 (d, J= 32.4 Hz), 109.44, 73.48, 56.09, 56.03, 53.16, 25.16, 19.18,9.27
115 ... ... ESIMS m/z 499.6 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 12.08 (d, J = 0.6 Hz, 1H), 8.32 (d, J= 9.4 Hz, 1H), 7.98 (d, 5= 5.2 Hz, 1H), 7.31 - 7.07 (m, 4H), 6.97 (t, J= 8.6 Hz, 2H), 6.93 - 6.86 (m, 3H), 5.72 (dq, J= 9.7, 6.2 Hz, 1H), 4.48 (dd, J= 9.4, 4.7 Hz, 1H), 4.05 (d, J = 9.7 Hz, 1H), 3.95 (s, 3H), 1.93-1.82 (m, 1H), 1.23 (d, J= 6.1 Hz, 3H), 0.82 (d, J= 6.9 Hz, 3H), 0.65 (d, J= 6.8 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 170.46, 168.95, 161.73 (d, J= 246.4 Hz), 161.65 (d,7= 245.6 Hz), 155.43, 148.71, 140.42, 136.85, 130.40, 129.54 (d, J= 4.7 Hz), 129.47 (d, J= 4.7 Hz), 115.71 (d, 7= 21.3 Hz), 115.40 (d, J= 21.3 Hz), 109.43, 73.51, 57.09, 56.09, 55.98, 30.96, 19.22, 19.10, 17.10
232
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
116 ... ... ESIMS m/z 513.7 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 12.07 (d, J = 0.6 Hz, 1H), 8.15 (d, 7= 8.9 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.31 - 7.04 (m, 4H), 7.08 - 6.74 (m, 6H), 5.70 (dq, 7= 10.0, 6.1 Hz, 1H), 4.54 (ddd, 7= 9.7, 8.8, 5.0 Hz, 1H), 4.04 (d, 7= 9.8 Hz, 1H), 3.94 (s, 3H), 1.46 - 1.36 (m, 1H), 1.33 1.18 (m,4H), 1.08 (ddd, 7= 13.9,9.0,5.0 Hz, 1H), 0.82 (d, 7= 6.5 Hz, 3H), 0.77 (d, 7= 6.6 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.62, 168.81, 161.75 (d, 7= 246.2 Hz), 161.66 (d, 7 = 245.6 Hz), 155.43, 148.74, 140.39, 137.02, 136.76, 130.34, 129.51 (d, 7= 3.4 Hz), 129.44 (d, 7= 3.5 Hz), 115.73 (d, 7= 21.4 Hz), 115.41 (d,7= 21.3 Hz), 109.44, 73.37, 56.21, 56.09, 50.52, 41.00, 24.57, 22.76, 21.49, 19.14
117 ... (Thin film) 3368, 2937, 1732, 1648, 1527, 1241, 1144 HRMS-ESI (m/z) ([M+H]+) calcd for C27H31N2O7, 495.2126; found, 495.2104 Ή NMR (300 MHz, CDC13) δ 12.15 (d,7 = 0.6 Hz, 1H), 8.38 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.45 (dd, 7= 7.6, 1.7 Hz, 1H), 7.30 - 7.20 (m, 1H), 7.12 (dddd, 7= 13.5,8.1,7.5, 1.7 Hz, 2H), 6.92 - 6.80 (m, 4H), 6.76 (dd, 7= 8.2, 1.1 Hz, 1H), 5.97 (dq, 7= 9.0, 5.7, 5.2 Hz, 1H), 5.01 (d,7= 10.1 Hz, 1H), 4.70 - 4.39 (m, 1H), 3.93 (s, 3H), 3.85 (s, 3H), 3.75 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.01 (d, 7= 7.2 Hz, 3H)
118 ... (Thin film) 3368, 2937, 1734, 1648, 1527, 1261, 1148, 1041 HRMS-ESI (m/z) ([M+H]+) calcd C27H31N2O7, 495.2126; found, 495.2106 Ή NMR (300 MHz, CDC13) δ 12.10 (d, 7 = 0.6 Hz, 1H), 8.35 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H),7.21 (t,7=8.0 Hz, 1H), 7.15 (t, 7= 7.9 Hz, 1H), 6.93 6.81 (m, 5H), 6.74 (ddd, 7= 8.2, 2.6, 0.9 Hz, 1H), 6.68 (ddd, 7= 8.2, 2.6, 0.9 Hz, 1H), 5.80 (dq, 7= 10.3, 6.1 Hz, 1H), 4.60 - 4.43 (m, 1H), 3.99 (d, 7= 10.3 Hz, 1H), 3.94 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 1.26 (d, 7= 6.0 Hz, 3H), 1.00 (d,7=7.2 Hz, 3H)
233
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
119 ... (Thin film) 3367, 2985, 1738, 1647, 1575, 1481, 1263, 1153, 1058,914 HRMS-ESI (m/z) ([M+H]+) calcd for C25H23C12F2N2O6, 555.0896; found, 555.0909 1H NMR (300 MHz, CDC13) δ 11.92 (s, 1H), 8.36 (d, J= 8.1 Hz, 1H), 7.95 (d, J= 5.2 Hz, 1H), 7.77 (t, J= 8.5 Hz, 1H), 7.37 (t, J= 8.5 Hz, 1H), 7.15 (ddd, J= 8.5, 2.1, 0.7 Hz, 1H), 7.08 - 6.89 (m, 3H), 6.86 (d, 7=5.3 Hz, 1H), 6.10 (q, 7= 6.2 Hz, 1H), 4.66 (p, J= 7.3 Hz, 1H), 3.95 (s, 3H), 3.22 (s, 1H), 1.36 (d, 7= 7.2 Hz, 3H), 1.24 (d, J= 6.3 Hz, 3H)
120 ... (Thin film) 3369, 2934, 1735, 1648, 1576, 1527, 1451, 1261 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O5, 499.2039; found, 499.2050 1H NMR (300 MHz, CDC13) δ 12.06 (d, J = 0.6 Hz, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.16 - 7.01 (m, 2H), 7.01 - 6.79 (m, 5H), 5.70 (dq, 7= 9.9, 6.1 Hz, 1H), 4.70 - 4.43 (m, 1H), 3.97 (d, 7= 9.3 Hz, 1H), 3.94 (s, 3H), 2.20 (d,7= 1.9 Hz, 3H), 2.17 (d, 7= 1.9 Hz, 3H), 1.25 (d, 7= 6.1 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H)
121 ... (Thin film) 3367, 2980, 1735, 1648, 1527, 1450, 1262, 1050 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29C12N2O5, 531.1448; found, 531.1458 Ή NMR (300 MHz, CDC13) 512.1411.95 (m, 1H), 8.33 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H),7.21 (d,7= 1.5 Hz, 2H), 7.19 - 6.99 (m, 4H), 6.86 (d, 7= 5.2 Hz, 1H), 5.69 (dq,7=9.8, 6.1Hz, 1H), 4.55 (p, 7= 7.3 Hz, 1H), 3.94 (d, 7= 9.9 Hz, 1H), 3.94 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.25 (d, 7= 6.0 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H)
122 ... (Thin film) 3367, 2986, 1737, 1647, 1611, 1482, 1452, 1215, 1148, 1057 HRMS-ESI (m/z) ([M+H]+) calcd for C25H25F2N2O6, 487.1675; found, 487.1686 1H NMR (300 MHz, CDC13) δ 12.00 (d, J = 0.6 Hz, 1H), 8.41 (d,7= 8.1 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.87 - 7.75 (m, 1H), 7.48 (tt, 7= 8.0, 1.5 Hz, 1H), 7.28 7.12 (m, 3H), 7.10 - 6.98 (m, 1H), 6.99 6.86 (m, 2H), 6.90 - 6.82 (m, 1H), 6.26 (qd, 7= 6.3, 1.5 Hz, 1H), 4.73 - 4.57 (m, 1H), 3.94 (s, 3H), 3.19 (dd, 7=2.8, 1.9 Hz, 1H), 1.28 (d, 7= 6.3 Hz, 3H), 1.27 (d, 7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -111.85 -112.11 (m),-112.15--112.47 (m)
234
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
123 ... (Thin film) 3285, 2981, 2107, 1736, 1648, 1528, 1263, 1050 HRMS-ESI (m/z) ([M+H]+) calcd for C29H27N2O5, 483.1914; found, 483.1919 Ή NMR (400 MHz, CDC13) δ 12.06 (d, J = 0.6 Hz, 1H), 8.33 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.45 - 7.40 (m, 2H), 7.40 - 7.35 (m, 2H), 7.28 - 7.18 (m, 4H), 6.86 (d, J= 5.2 Hz, 1H), 5.78 (dq, J = 9.8, 6.1Hz, 1H), 4.61-4.45 (m, 1H), 4.07 (d, J= 9.8 Hz, 1H), 3.94 (s, 3H), 3.05 (s, 1H), 3.03 (s, 1H), 1.25 (d,7=6.2 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H)
124 ... (Thin film) 3368, 2963, 1735, 1648, 1527, 1480, 1450, 1280, 1263, 1142, 1053 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O5, 491.2540; found, 491.2551 'H NMR (400 MHz, CDC13) δ 12.12 (s, 1H), 8.37 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.24 - 7.18 (m, 4H), 7.14 7.08 (m, 2H), 7.08 - 7.02 (m, 2H), 6.85 (d, 7= 5.2 Hz, 1H), 5.80 (dq,7= 10.1, 6.2 Hz, 1H), 4.63 - 4.40 (m, 1H), 3.99 (d, 7= 10.2 Hz, 1H), 3.93 (s, 3H), 2.65 2.50 (m, 4H), 1.25 (d,7= 6.1 Hz, 3H), 1.18 (t, 7= 7.6 Hz, 3H), 1.14 (t, 7=7.6 Hz, 3H), 0.94 (d, 7= 7.2 Hz, 3H)
125 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C25H215FN2O5, 453.1820; found, 453.1831 Ή NMR (400 MHz, CDC13) δ 12.08 (d, J = 0.6 Hz, 1H), 8.33 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.32 - 7.20 (m, 5H), 7.19-7.10 (m, 1H), 6.97 (t, 7= 8.7 Hz, 2H), 6.86 (d, 7= 5.2 Hz, 1H), 5.78 (dq, 7= 10.0, 6.2 Hz, 1H), 4.58 - 4.45 (m, 1H), 4.05 (d, 7= 10.0 Hz, 1H), 3.94 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 0.98 (d, 7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.63, 168.54, 161.72 (d, 7= 245.7 Hz), 155.35, 148.71, 141.10, 140.41, 136.91 (d,7= 3.5 Hz), 130.42, 129.58 (d, 7= 7.8 Hz), 128.59, 127.95, 126.84, 115.64 (d,7= 21.3 Hz), 109.40, 73.39, 57.04, 56.07, 47.83, 19.15, 17.59
235
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Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
127 ... ... ESIMS m/z 589.5 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 11.77 (d, J = 0.6 Hz, 1H), 8.25 (d, J= 8.0 Hz, 1H), 7.96 (d, J= 5.2 Hz, 1H), 7.53 (dd, J= 20.0, 2.2 Hz, 2H), 7.35 (dd, 7= 8.5, 1.8 Hz, 2H), 7.18 (ddd, 7= 10.9,8.5,2.3 Hz, 2H), 6.88 (d, 7= 5.2 Hz, 1H), 5.80 (q, 7= 6.3 Hz, 1H), 4.68 - 4.47 (m, 1H), 3.95 (s, 3H), 1.27 (d, 7= 7.3 Hz, 3H), 1.20 (d, 7= 6.4 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 170.98, 168.86, 155.52, 148.74, 144.18, 141.99, 140.57, 132.92, 132.87, 132.02, 131.86, 130.48, 130.37, 129.91, 128.15, 127.74, 125.09, 124.82, 109.64, 78.58, 74.60, 56.11,48.05, 17.56, 14.13
128 ... ... ESIMS m/z 555.6 ([M+H]+) Ή NMR (400 MHz, CDC13) δ 11.78 (d, 7 = 0.6 Hz, 1H), 8.25 (d, 7= 8.0 Hz, 1H), 7.96 (d, 7= 5.3 Hz, 1H), 7.33 - 7.27 (m, 2H), 7.22 (dd, 7= 10.4, 2.2 Hz, 1H), 7.08 (dddd, 7= 19.0, 8.5, 2.1, 0.8 Hz, 2H), 6.88 (d, 7= 5.2 Hz, 1H), 5.82 (q, 7= 6.3 Hz, 1H), 4.65-4.51 (m, 1H), 3.95 (s, 3H), 3.00 (s, 1H), 1.26 (d, 7= 7.2 Hz, 3H), 1.20 (d, 7= 6.3 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 170.92, 168.87, 158.04 (d, 7= 249.8 Hz), 157.99 (d, 7= 249.5 Hz), 155.54, 148.76, 145.02 (d, 7= 5.5 Hz), 142.77 (d, 7= 6.0 Hz), 140.55, 130.65, 130.55, 129.94, 122.05 (d, 7= 3.7 Hz), 121.65 (d, 7= 3.6 Hz), 120.45 (d,7= 17.8 Hz), 120.25 (d,7= 17.7 Hz), 114.56 (d, 7= 22.7 Hz), 114.26 (d, 7= 23.0 Hz), 109.62, 78.63, 74.64, 56.12, 48.02, 17.52, 14.30
236
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
129 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H29CI2N2O5, 531.1448; found, 531.1454 'H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.32 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.25 (d, J= 9.7 Hz, 1H), 7.19 (d, J= 8.2 Hz, 1H), 7.09 (dd, J= 4.0, 2.3 Hz, 2H), 7.02 (td, 7= 8.5, 2.3 Hz, 2H), 6.87 (d, 7= 5.2 Hz, 1H),5.71 (dq,7 = 10.0, 6.1 Hz, 1H), 4.54 (p,7= 7.3 Hz, 1H), 3.99 - 3.92 (m, 4H), 2.33 (s, 3H), 2.29 (s, 3H), 1.24 (d,7= 6.1 Hz, 3H), 1.07 (d,7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.61, 168.57, 155.39, 148.74, 140.44, 139.53, 139.35, 136.56, 136.15, 133.12, 132.77, 130.63, 130.59, 130.34, 129.45, 129.12, 126.59, 126.41, 109.44, 73.05, 56.45, 56.08,47.85,20.17, 20.08, 19.15, 17.69
237
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
130 ... (Thin film) 3376, 2986, 2360, 2107, 1736, 1652, 1604, 1558, 1530, 1508, 1452, 1427, 1381, 1329, 1287, 1262, 1247, 1223, 1187, 1159, 1137, 1116, 1049, 1015,911, 826, 792, 779, 729, 680, 668 HRMS-ESI (m/z) ([M+H]+) calcd for €’24^26^2^04. 521.0709; found, 521.0713 'H NMR (400 MHz, CDC13) δ 12.63 (s, 1H), 8.32 (d, J= 7.9 Hz, 1H), 7.88 (d, J= 4.9 Hz, 1H), 7.62 (d, J= 4.9 Hz, 1H), 7.29 - 7.15 (m, 4H), 7.05 - 6.85 (m, 4H), 5.74 (dq, J= 9.9, 6.2 Hz, 1H), 4.61 4.48 (m, 1H), 4.05 (d, J= 9.9 Hz, 1H), 1.25 (d, 7= 6.1 Hz, 3H), 1.06 (d,7=7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 171.39, 167.69, 161.76 (d, J= 246.1 Hz), 161.65 (d, J= 246.0 Hz), 155.39, 139.43, 136.82 (d, 7= 3.4 Hz), 136.63 (d,7=3.1Hz), 132.21, 131.44, 129.47 (d, 7= 8.0 Hz), 129.44 (d, 7= 7.9 Hz), 122.15, 115.76 (d, 7= 21.3 Hz), 115.42 (d, 7= 21.3 Hz), 73.47,56.15,48.05, 19.11, 17.61 19F NMR (471 MHz, CDC13) δ -115.26 -115.47 (m), -115.64 (ddd, 7= 13.7, 8.9, 5.2 Hz)
238
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
131 ... (Thin film) 3373, 2940, 1739, 1651, 1609, 1577, 1518, 1481, 1454, 1436, 1382, 1324, 1283, 1243, 1210, 1149, 1120, 1054, 954, 924, 872, 850, 824, 801,754, 733 HRMS-ESI (m/z) ([M+H]+) calcd for C25H23F4N2O5, 507.1538; found, 507.1543 'H NMR (300 MHz, CDCfi) δ 12.01 (d, J = 0.6 Hz, 1H), 8.31 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.18 - 6.91 (m, 5H), 6.88 (d, 7= 5.2 Hz, 1H), 5.66 (dq, J = 9.4, 6.2 Hz, 1H), 4.64 - 4.49 (m, 1H), 4.01 (d, 7= 9.4 Hz, 1H), 3.95 (s, 3H), 1.32-1.21 (m, 4H), 1.16 (d, 7= 7.2 Hz, 3H) 19FNMR(471 MHz, CDCfi) δ -136.05 -136.27 (m),-136.61 (ddd, 7= 20.1, 11.4, 8.1Hz),-139.14--139.32 (m), -139.45--139.68 (m)
239
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
132 ... (Thin film) 3372, 2983, 1737, 1649, 1601, 1576, 1529, 1498, 1481, 1453, 1439, 1381, 1323, 1245, 1184, 1145, 1096, 1060, 953, 909, 864, 849, 824, 800, 730, 689 HRMS-ESI (m/z) ([M+H]+) calcd for C25H23CI2F2N2O5, 539.0947; found, 539.0954 1H NMR (300 MHz, CDCfi) δ 12.02 (d, J = 0.6 Hz, 1H), 8.31 (d, J= 7.9 Hz, 1H), 7.97 (d, J= 5.2 Hz, 1H), 7.27 (td, J= 7.3, 2.1 Hz, 2H), 7.19- 6.98 (m, 4H), 6.88 (d, 7=5.2 Hz, 1H), 5.66 (dq,7=9.5, 6.1Hz, 1H), 4.66 - 4.48 (m, 1H), 4.01 (d, 7= 9.6 Hz, 1H), 3.95 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 1.17 (d, 7= 7.2 Hz, 3H) 19FNMR(471 MHz, CDCfi) δ -116.83 -116.94 (m), -117.22 - -117.34 (m)
240
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
133 ... (Thin film) 3372, 2935, 2257, 1735, 1649, 1576, 1528, 1501, 1481, 1452, 1439, 1380, 1324, 1281, 1262, 1241, 1206, 1149, 1118, 1051,952, 908, 849, 821, 800, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O5, 499.2039; found, 499.2046 'H NMR (300 MHz, CDCfi) δ 12.08 (d, J = 0.5 Hz, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.97 (d, J= 5.2 Hz, 1H), 7.12 - 6.98 (m, 5H), 6.97 - 6.79 (m, 3H), 5.70 (dq, J= 10.1,6.1 Hz, 1H), 4.65 - 4.46 (m, 1H), 3.94 (s, 3H),2.21 (dd,J=9.8, 1.9 Hz, 6H), 1.24 (d,7=6.1Hz, 3H), 1.06 (d,7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -119.78 -120.04 (m), -120.30 - -120.53 (m)
135 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C25H25F2N2O5, 471.1726; found, 471.1742 'H NMR (300 MHz, CDC13) δ 12.08 (d, J = 0.6 Hz, 1H), 8.20 (d, J= 8.0 Hz, 1H), 8.00 (d, 7= 5.2 Hz, 1H), 7.26 - 7.13 (m, 4H), 7.02 - 6.83 (m, 5H), 5.69 (dq, 7= 9.0, 6.2 Hz, 1H), 4.53 (dq, 7= 8.0, 7.2 Hz, 1H), 4.05 (d,7=9.1 Hz, 1H),3.96 (s, 3H), 1.34 (d, 7= 7.2 Hz, 3H), 1.22 (d, 7= 6.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.27, 168.54, 162.68, 162.58, 160.73, 160.63, 155.43, 148.77, 140.44, 136.81, 136.78, 136.46, 136.43, 130.33, 129.72, 129.66, 129.63, 129.57, 115.74, 115.57, 115.43, 115.26, 109.49, 73.33, 56.11, 55.65, 47.80, 18.95, 17.74
241
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
136 — — HRMS-ESI (m/z) ([M+H]+) calcd for C25H23CI4N2O5, 571.0356; found, 571.0367 'H NMR (300 MHz, CDC13) δ 12.00 (s, 1H), 8.30 (d, J= 7.8 Hz, 1H), 7.98 (d, J= 5.1 Hz, 1H), 7.42 - 7.28 (m, 4H), 7.09 (ddd, J= 10.1, 8.3, 2.2 Hz, 2H), 6.87 (d, 7=5.2 Hz, 1H), 5.65 (dt,7= 12.2,6.1 Hz, 1H), 4.57 (p, 7= 7.3 Hz, 1H), 4.00 (d, 7= 9.6 Hz, 1H), 3.95 (s, 3H), 1.27 (d, 7=5.9 Hz, 3H), 1.17 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.45, 168.64, 155.42, 148.74, 140.51, 140.21, 140.16, 133.11, 132.76, 131.70, 131.38, 130.97, 130.67, 130.27, 130.20, 130.08, 127.25, 127.17, 109.53, 72.38, 56.09, 55.71,47.87, 19.03, 17.71
137 — — HRMS-ESI (m/z) ([M+H]+) calcd for C25H23CI2F2N2O5, 539.0947; found, 539.0953 1H NMR (300 MHz, CDC13) δ 11.99 (s, 1H), 8.30 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.42 - 7.19 (m, 2H), 7.08 6.94 (m, 4H), 6.90 - 6.84 (m, 1H), 5.67 (dq, 7= 9.4, 6.2 Hz, 1H), 4.65 - 4.48 (m, 1H), 4.03 (d, 7= 9.4 Hz, 1H), 3.95 (s, 3H), 1.27 (d,7=6.1Hz, 3H), 1.16 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.41, 168.64, 158.16 (d, 7= 250.2 Hz), 158.01 (d, 7 = 250.1 Hz), 155.42, 148.75, 140.91 (d,7=6.1Hz), 140.83 (d, 7= 6.3 Hz), 140.51, 131.12, 130.81, 130.20, 124.67123.96 (m), 120.11 (d,7= 17.5 Hz), 119.82 (d, 7= 17.7 Hz), 116.78 - 116.06 (m), 109.52, 72.44, 56.09, 47.85, 18.99, 17.71
242
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
138 ... ... HRMS-ESI (m/z) [M]+ calcd for C28H30N2O8, 522.2002; found, 522.2006 'HNMR (500 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.13 (d, 7= 8.0 Hz, 1H), 7.50 - 7.44 (m, 4H), 7.27 (ddd, 7= 11.5, 8.5, 7.0 Hz, 4H), 7.20 - 7.14 (m, 2H), 6.94 (d, 7= 5.4 Hz, 1H), 6.01 (q, 7= 6.3 Hz, 1H), 5.75 - 5.62 (m, 2H), 4.63 - 4.52 (m, 1H), 3.90 (s, 3H), 2.94 (s, 1H), 2.06 (s, 3H), 1.22 (d,7= 6.3 Hz, 3H), 1.03 (d, 7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.88, 170.27, 163.03, 160.26, 145.73, 144.99, 143.90, 142.88, 142.57, 128.31, 128.28, 127.14, 127.07, 125.56, 125.54, 109.58, 89.49, 79.55, 75.21, 56.19, 48.10, 30.93, 20.87, 17.75, 14.36
139 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H29N2O6, 477.2025; found, 477.2019 Ή NMR (400 MHz, CDC13) δ 8.41 (d, 7 = 7.8 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.38-7.10 (m, 10H), 6.97 (d, 7= 5.4 Hz, 1H), 5.82 (dq, 7= 10.0, 6.2 Hz, 1H), 4.52 (dt,7= 8.2, 7.1 Hz, 1H), 4.05 (d,7= 10.1 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.24 (d, 7= 6.1 Hz, 3H), 0.89 (d, 7= 7.1 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.23, 168.89, 162.28, 159.42, 146.66, 141.55, 141.44, 141.25, 137.45, 128.77, 128.50, 128.13, 128.11, 126.89, 126.67, 109.73, 73.32, 57.90, 56.27, 47.85, 20.75, 19.25, 17.92
243
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
140 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H33N2O6, 505.2338; found, 505.2324 'HNMR (400 MHz, CDC13) δ 8.35 (d, J = 7.7 Hz, 1H), 8.30 (d, J= 5.4 Hz, 1H), 7.34 - 7.09 (m, 10H), 6.95 (d, J= 5.5 Hz, 1H), 5.81 (dq, 7= 10.0, 6.2 Hz, 1H), 4.62 - 4.44 (m, 1H), 4.05 (d, J= 10.0 Hz, 1H), 3.85 (s, 3H), 2.93 (hept, J= 7.0 Hz, 1H), 1.34 (d, 7= 7.0 Hz, 6H), 1.24 (d,7=6.2 Hz, 3H), 0.88 (d, 7= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 174.69, 172.33, 162.28, 159.39, 146.56, 141.95, 141.45, 141.27, 137.61, 128.76, 128.50, 128.14, 128.12, 126.89, 126.67, 109.58, 73.28, 57.90, 56.27, 47.83, 33.94, 19.24, 18.82, 17.96
141 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H31N2O7, 507.2131; found, 507.2125 'HNMR (400 MHz, CDC13) δ 8.25 (d, J = 5.4 Hz, 1H), 8.22 (d, 7= 7.9 Hz, 1H), 7.34 - 7.09 (m, 10H), 6.92 (d, 7= 5.4 Hz, 1H), 5.83 (dq, 7= 10.1, 6.2 Hz, 1H), 5.72 (d, 7= 0.7 Hz, 2H), 4.60 - 4.49 (m, 1H), 4.06 (d,7= 10.1 Hz, 1H), 3.88 (s, 3H), 2.05 (s, 3H), 1.25 (d,7= 6.1 Hz, 3H), 0.91 (d, 7=7.2 Hz, 3H) 13CNMR(101 MHz, CDCh) δ 172.33, 170.25, 162.88, 160.24, 145.70, 143.91, 142.54, 141.48, 141.25, 128.76, 128.49, 128.12, 128.09, 126.89, 126.65, 109.56, 89.50, 73.27, 57.92, 56.17, 48.07, 20.86, 19.25, 17.73
244
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
142 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O7, 535.2444; found, 535.2431 'HNMR (400 MHz, CDC13) δ 8.28 (d, J = 7.9 Hz, 1H), 8.25 (d, J= 5.3 Hz, 1H), 7.36 - 7.08 (m, 10H), 6.92 (d, J= 5.4 Hz, 1H), 5.83 (dq, J= 10.1, 6.2 Hz, 1H), 5.79 - 5.69 (m, 2H), 4.62 - 4.44 (m, 1H), 4.06 (d,7= 10.1 Hz, 1H), 3.86 (s, 3H),2.53 (hept, 7= 7.0 Hz, 1H), 1.25 (d,7=6.2 Hz, 3H), 1.13 (d, 7= 7.0 Hz, 6H),0.91 (d, 7= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 176.22, 172.34, 162.85, 160.23, 145.55, 144.16, 142.18, 141.48, 141.26, 128.76, 128.49, 128.12, 128.09, 126.89, 126.65, 109.48, 89.90, 73.26, 57.93, 56.12, 48.07, 33.85, 19.26, 18.68, 17.74
143 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C23H25N2O6S2, 489.1154; found, 489.1154 Ή NMR (400 MHz, CDC13) δ 8.49 (d, J = 8.1 Hz, 1H), 8.31 (d,7= 5.5 Hz, 1H), 7.21 - 7.13 (m, 2H), 7.03 - 6.97 (m, 2H), 6.95 - 6.86 (m, 3H), 5.54 (dq, 7= 7.3, 6.2 Hz, 1H), 4.70 - 4.61 (m, 2H), 3.88 (s, 3H), 2.39 (s, 3H), 1.28 (d, 7= 6.2 Hz, 3H), 1.17 (d, 7= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.03, 168.89, 162.33, 159.44, 146.66, 143.85, 142.75, 141.50, 137.48, 126.75, 126.56, 126.06, 125.43, 124.60, 124.55, 109.78, 74.58, 56.28, 47.96, 47.41, 20.76, 18.68, 18.14
144 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C24H27N2O7S2, 519.1259; found, 519.1258 Ή NMR (400 MHz, CDC13) δ 8.30 (d, J = 7.9 Hz, 1H), 8.26 (d, 7= 5.4 Hz, 1H), 7.21 - 7.13 (m, 2H), 7.02 (ddd, 7= 3.5, 1.2, 0.6 Hz, 1H), 6.96 - 6.88 (m, 4H), 5.73 (d, 7= 0.7 Hz, 2H), 5.55 (dq, 7= 7.4, 6.2 Hz, 1H), 4.75 - 4.60 (m, 2H), 3.89 (s, 3H), 2.06 (s, 3H), 1.29 (d,7= 6.3 Hz, 3H), 1.19 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 172.13, 170.25, 162.91, 160.26, 145.69, 143.96, 143.86, 142.81, 142.46, 126.74, 126.55, 126.03, 125.42, 124.58, 124.54, 109.59, 89.52, 74.55, 56.19, 48.18, 47.42, 20.87, 18.70, 17.95
245
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
145 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27F2N2O6, 513.1837; found, 513.1835 'HNMR (400 MHz, CDCfi) δ 8.48 8.37 (m, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.29 - 7.18 (m, 4H), 7.05 - 6.90 (m, 5H), 5.72 (dq, 7= 9.7, 6.2 Hz, 1H), 4.55 (dq, J = 8.3, 7.2 Hz, 1H), 4.05 (d, 7= 9.6 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.22 (d, J = 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCfi) δ -115.58,-115.93
146 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1943; found, 543.1938 'HNMR (400 MHz, CDCfi) δ 8.26 (d, J = 5.4 Hz, 1H), 8.22 (d, 7= 7.8 Hz, 1H), 7.32 - 7.16 (m, 4H), 7.05 - 6.89 (m, 5H), 5.78 - 5.68 (m, 1H), 5.72 (s, 2H), 4.64 4.50 (m, 1H), 4.06 (d, 7= 9.7 Hz, 1H), 3.90 (s, 3El), 2.06 (s, 3H), 1.24 (d,7= 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCfi) δ -115.59,-115.97
147 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O8, 551.2393; found, 551.2396 'HNMR (400 MHz, CDCfi) δ 8.34 (d, J = 7.9 Hz, 1H), 8.25 (d, 7= 5.4 Hz, 1H), 7.39-7.16 (m, 10H), 6.94 (d, 7= 5.4 Hz, 1H), 5.97 (q, 7= 6.2 Hz, 1H), 5.78 - 5.61 (m, 2H), 4.74 - 4.56 (m, 1H), 3.90 (s, 3H), 3.42 (dq, 7=9.2, 7.0 Hz, 1H), 3.21 (dq,7= 9.2, 7.0 Hz, 1H), 2.05 (s, 3H), 1.25 (d,7= 7.2Hz, 3H), 1.19 (t,7=6.9 Hz, 3H), 1.12 (d, 7= 6.3 Hz, 3H) 13CNMR(101 MHz, CDCfi) δ 172.13, 170.23, 162.87, 160.27, 145.64, 144.02, 142.35, 142.09, 140.72, 128.24, 127.84, 127.81, 127.70, 127.27, 127.18, 109.57, 89.52, 84.04, 74.08, 59.96, 56.18, 48.26, 20.86, 18.23, 15.70, 14.95
246
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
148 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H27F4N2O7, 579.1754; found, 579.1756 'HNMR (400 MHz, CDC13) δ 8.26 (d, J = 5.3 Hz, 1H), 8.22 (d, J= 7.8 Hz, 1H), 7.38 (td, J= 8.6, 6.2 Hz, 1H), 7.24 (td, J = 8.4, 6.3 Hz, 1H), 6.96 (d, J= 5.5 Hz, 1H), 6.88 - 6.69 (m, 4H), 5.88 - 5.75 (m, 1H), 5.73 (s, 2H), 4.69 (d, J= 9.8 Hz, 1H), 4.65 - 4.55 (m, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.29 (d, J= 6.2 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -111.11 (d, 7= 7.6 Hz),-111.57 (d, 7= 7.5 Hz), -111.99 (dd, 7= 7.7, 2.6 Hz), 112.76 (dd, 7= 7.6, 2.5 Hz)
149 ... ... HRMS-ESI (m/z) [M-OCH3]+ calcd for C28H29N2O7, 505.1975; found, 505.1975 'HNMR (400 MHz, CDC13) δ 8.33 (d, J = 7.9 Hz, 1H), 8.25 (d, 7= 5.4 Hz, 1H), 7.40-7.18 (m, 10H), 6.94 (d, 7= 5.4 Hz, 1H), 5.97 (q, 7= 6.2 Hz, 1H), 5.81 - 5.63 (m, 2H), 4.72 - 4.52 (m, 1H), 3.90 (s, 3H), 3.17 (s, 3H), 2.05 (s, 3H), 1.24 (d,7 = 7.2 Hz, 3H), 1.12 (d, 7= 6.3 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.09, 170.24, 162.88, 160.27, 145.65, 144.02, 142.35, 141.39, 140.04, 128.50, 128.08, 127.87, 127.71, 127.45, 127.28, 109.57, 89.53, 84.46, 73.81, 56.19, 52.59, 48.25, 20.86, 18.18, 14.98
150 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H25F4N2O6, 549.1648; found, 549.1645 'HNMR (400 MHz, CDC13) δ 8.39 (d, J = 8.1 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.37 (td,7= 8.5, 6.1 Hz, 1H), 7.23 (td,7 = 8.5, 6.2 Hz, 1H), 7.00 (d, 7= 5.5 Hz, 1H), 6.90 - 6.68 (m, 4H), 5.89 - 5.71 (m, 1H), 4.69 (d, 7= 9.8 Hz, 1H), 4.62 - 4.51 (m, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.28 (d, 7= 6.2 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -111.11 (d, 7= 7.7 Hz),-111.55 (d,7= 7.5 Hz), -112.01 (dd, 7= 7.7, 2.6 Hz), 112.80 (dd, 7= 7.6, 2.6 Hz)
247
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
152 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H28FN2O6, 495.1931; found, 495.1926 'HNMR (400 MHz, CDC13) δ 8.38 (d, J = 8.2 Hz, 1H), 8.30 (d, J= 5.4 Hz, 1H), 7.50 - 7.37 (m, 4H), 7.37 - 7.19 (m, 6H), 6.98 (d, J= 5.5 Hz, 1H), 5.98 (dq, J= 25.1, 6.4 Hz, 1H), 4.63 - 4.54 (m, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.30 (d,7= 6.5 Hz, 3H), 0.88 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -168.48
153 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O7, 525.2037; found, 525.2033 'HNMR (400 MHz, CDC13) δ 8.26 (d, J = 5.3 Hz, 1H), 8.20 (d, 7= 7.7 Hz, 1H), 7.49 _ 7.40 (m, 4H), 7.36 - 7.21 (m, 6H), 6.93 (d, 7= 5.5 Hz, 1H), 5.99 (dq, 7= 25.2, 6.4 Hz, 1H), 5.71 (s, 2H), 4.68 - 4.49 (m, 1H), 3.89 (s, 3H), 2.05 (s, 3H), 1.31 (d, 7= 6.5 Hz, 3H), 0.90 (d,7=7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -168.67
155 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H33N2O8, 537.2237; found, 537.2226 'HNMR (400 MHz, CDC13) δ 8.42 (d, J = 8.1 Hz, 1H), 8.30 (d,7= 5.4 Hz, 1H), 7.26 - 7.13 (m, 4H), 6.97 (d,7= 5.5 Hz, 1H), 6.85 - 6.71 (m, 4H), 5.71 (dq,7= 9.9, 6.2 Hz, 1H), 4.64 - 4.47 (m, 1H), 3.96 (d, 7= 9.8 Hz, 1H), 3.87 (s, 3H), 3.74 (s, 3H), 3.72 (s, 3H), 2.38 (s, 3H), 1.22 (d, 7= 6.1 Hz, 3H), 0.98 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 172.21, 168.88, 162.28, 159.42, 158.33, 158.20, 146.66, 141.53, 137.43, 133.90, 133.82, 129.02, 129.00, 114.09, 113.83, 109.74, 73.54, 56.26, 56.08, 55.19, 47.90, 20.74, 19.22, 18.08
248
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
156 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27F2N2O6, 513.1837; found, 513.1833 'HNMR (400 MHz, CDC13) δ 8.41 (d, J = 7.6 Hz, 1H), 8.31 (d, 7= 5.5 Hz, 1H), 7.32 - 7.18 (m, 2H), 7.12 - 6.82 (m, 7H), 5.73 (dq, 7= 9.7, 6.2 Hz, 1H), 4.64 4.43 (m, 1H), 4.06 (d, 7= 9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.25 (d,7= 6.2 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -112.15,-112.56
157 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27CI2N2O6, 545.1246; found, 545.1239 'HNMR (400 MHz, CDC13) δ 8.41 (d, 7 = 7.7 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.31 - 7.10 (m, 8H), 6.99 (d,7= 5.5 Hz, 1H), 5.72 (dq, 7= 9.8, 6.0 Hz, 1H), 4.59 - 4.50 (m, 1H), 4.01 (d, 7= 9.8 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.24 (d,7= 6.1 Hz, 3H), 1.00 (d, 7= 7.1 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 172.10, 168.87, 162.33, 159.43, 146.68, 142.60, 142.44, 141.40, 137.46, 134.67, 134.38, 130.21, 129.95, 128.46, 128.34, 128.10, 127.45, 127.17, 126.23, 126.13, 109.80, 72.61, 56.98, 56.28, 47.82, 20.75, 19.12, 17.98
158 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O9, 567.2342; found, 567.2338 'HNMR (400 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 8.23 (d, 7= 8.0 Hz, 1H), 7.24-7.14 (m, 4H), 6.93 (d, 7= 5.4 Hz, 1H), 6.85 - 6.75 (m, 4H), 5.77 - 5.68 (m, 1H), 5.72 (s, 2H), 4.63 - 4.50 (m, 1H), 3.97 (d, 7= 9.9 Hz, 1H), 3.89 (s, 3H), 3.75 (s, 3H), 3.73 (s, 3H), 2.05 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.34, 170.24, 162.88, 160.24, 158.33, 158.20, 145.70, 143.91, 142.54, 133.95, 133.82, 129.00, 114.09, 113.83, 109.55, 89.51, 73.49, 56.17, 56.10, 55.20, 48.12, 20.85, 19.23, 17.90
249
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
159 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1943; found, 543.1941 'HNMR (400 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 8.23 (d, J= 7.9 Hz, 1H), 7.32 - 7.18 (m, 2H), 7.14 - 7.03 (m, 2H), 7.04 - 6.80 (m, 5H), 5.82 - 5.67 (m, 1H), 5.72 (s, 2H), 4.65 - 4.48 (m, 1H), 4.07 (d, J= 9.9 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.26 (d, 7=6.1 Hz, 3H), 1.00 (d,7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -112.16,-112.59
160 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29CI2N2O7, 575.1352; found, 575.1349 'HNMR (400 MHz, CDC13) δ 8.26 (d, J = 5.3 Hz, 1H), 8.22 (d, J= 7.6 Hz, 1H), 7.33 - 7.10 (m, 8H), 6.94 (d,7= 5.4 Hz, 1H), 5.80 - 5.65 (m, 1H), 5.72 (s, 2H), 4.60 - 4.52 (m, 1H), 4.03 (d, 7= 9.8 Hz, 1H), 3.90 (s, 3H), 2.06 (d,7= 1.8 Hz, 3H), 1.26 (d, 7= 6.0 Hz, 3H), 1.02 (d, 7= 7.1Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.34, 170.24, 162.88, 160.24, 158.33, 158.20, 145.70, 143.91, 142.54, 133.95, 133.82, 129.00, 114.09, 113.83, 109.55, 89.51, 73.49, 56.17, 56.10, 55.20, 48.12, 20.85, 19.23, 17.90
161 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27N2O6, 475.1869; found, 475.1865 Ή NMR (400 MHz, CDC13) δ 8.77 8.53 (m, 1H), 8.40 - 8.29 (m, 1H), 7.79 7.62 (m, 3H), 7.61 - 7.47 (m, 1H), 7.47 7.34 (m, 2H), 7.34 - 7.20 (m, 2H), 7.05 6.94 (m, 1H), 5.83 - 5.66 (m, 1H), 4.93 4.77 (m, 1H), 4.37 - 4.21 (m, 1H), 3.89 (s, 3H), 2.47 - 2.37 (m, 3H), 1.63 - 1.47 (m, 3H), 0.84 - 0.67 (m, 3H)
162 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27N2O7, 491.1818; found, 491.1813 'H NMR (400 MHz, CDC13) δ 8.58 8.43 (m, 1H), 8.40 - 8.32 (m, 1H), 7.36 7.19 (m, 4H), 7.13 - 7.03 (m, 4H), 7.02 6.97 (m, 1H), 5.17 - 5.05 (m, 1H), 4.77 4.64 (m, 1H), 4.35 - 4.19 (m, 1H), 3.96 3.85 (m, 3H), 2.40 (d, J= 3.6 Hz, 3H), 1.50 - 1.41 (m, 3H), 1.07 - 0.93 (m, 3H)
250
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
163 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29N2O7, 505.1975; found, 505.1961 Ή NMR (400 MHz, CDC13) δ 8.52 8.37 (m, 1H), 8.32 - 8.24 (m, 1H), 7.80 - 7.63 (m, 3H), 7.61 - 7.47 (m, 1H), 7.45 7.22 (m, 4H), 7.01 - 6.92 (m, 1H), 5.83 5.68 (m, 3H), 4.97 - 4.73 (m, 1H), 4.38 4.19 (m, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 1.64 - 1.49 (m, 3H), 0.90 - 0.66 (m, 3H)
164 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29N2O8, 521.1924; found, 521.1913 'HNMR (400 MHz, CDC13) δ 8.39 8.25 (m, 2H), 7.39 - 7.20 (m, 4H), 7.15 7.00 (m,4H), 6.99-6.92 (m, 1H),5.815.72 (m,2H), 5.16 -5.09 (m, 1H),4.794.67 (m, 1H), 4.37 - 4.17 (m, 1H), 3.91 (s, 3H), 2.08 (s, 3H), 1.51-1.43 (m, 3H), 1.09-0.93 (m, 3H)
165 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for CfvffivBnYOg. 633.0236; found, 633.0230 Ή NMR (400 MHz, CDC13) δ 8.39 (d, J = 6.8 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.45 - 7.31 (m, 4H), 7.18 - 7.06 (m, 4H), 7.00 (d, 7= 5.5 Hz, 1H), 5.71 (dq, 7= 9.5, 6.2 Hz, 1H), 4.65 - 4.46 (m, 1H), 4.00 (d, 7= 9.5 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 1.02 (d,7=7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.05, 168.89, 162.33, 159.47, 146.65, 141.39, 139.74, 139.71, 137.49, 131.97, 131.68, 129.89, 129.78, 121.06, 120.79, 109.84, 72.56, 56.41, 56.30, 47.83, 20.76, 19.09, 17.98
251
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¥, 13C, 19F)
166 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C25H29N2O6S2, 517.1467; found, 517.1465 'HNMR (400 MHz, CDCf) δ 8.51 (d, J = 8.1 Hz, 1H), 8.32 (d,7= 5.4 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.74 (d, 7= 3.4 Hz, 1H), 6.67 (d, 7= 2.6 Hz, 1H), 6.60 6.42 (m, 2H), 5.53 - 5.39 (m, 1H), 4.72 4.58 (m, 1H), 4.44 (d, 7= 7.1 Hz, 1H), 3.88 (s, 3H), 2.41 - 2.38 (m, 9H), 1.27 (d, 7= 6.2 Hz, 3H), 1.22 (d, 7= 7.2 Hz, 3H) 13C NMR (101 MHz, CDCf) δ 172.07, 168.90, 162.33, 159.44, 146.66, 141.64, 141.56, 140.54, 138.98, 138.92, 137.47, 125.77, 125.08, 124.66, 124.42, 109.76, 74.45, 56.28, 48.01, 47.83, 20.75, 18.64, 18.21, 15.25
167 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H33N2O6, 505.2338; found, 505.2345 'HNMR (400 MHz, CDCf) δ 8.42 (d, J = 8.0 Hz, 1H), 8.29 (d, 7= 5.4 Hz, 1H), 7.20 - 7.10 (m, 4H), 7.10 - 6.99 (m, 4H), 6.96 (d, 7= 5.5 Hz, 1H), 5.77 (dq, 7= 10.0, 6.2 Hz, 1H), 4.65 - 4.45 (m, 1H), 3.98 (d, 7= 10.0 Hz, 1H), 3.85 (s, 3H), 2.37 (s, 3H), 2.26 (s, 3H), 2.23 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.93 (d, 7= 7.1 Hz, 3H) 13C NMR (101 MHz, CDCf) δ 172.23, 168.90, 162.28, 159.42, 146.67, 141.58, 138.67, 138.57, 137.44, 136.33, 136.02, 129.41, 129.11, 127.94, 127.91, 109.74, 73.44, 57.06, 56.27, 47.91, 20.97, 20.94, 20.76, 19.26, 17.99
252
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
168 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O6, 533.2651; found, 533.2655 'HNMR (400 MHz, CDCfi) δ 8.36 (d, J = 8.8 Hz, 1H), 8.29 (d, J= 5.4 Hz, 1H), 7.19 - 7.12 (m, 4H), 7.10 - 6.98 (m, 4H), 6.94 (d, J= 5.5 Hz, 1H), 5.76 (dq, J= 10.0, 6.2 Hz, 1H), 4.60 - 4.45 (m, 1H), 3.97 (d, J= 9.9 Hz, 1H), 3.84 (s, 3H), 3.00 - 2.85 (m, 1H), 2.26 (s, 3H), 2.24 (s, 3H), 1.34 (d, J= 7.0 Hz, 6H), 1.22 (d, J= 6.1 Hz, 3H), 0.93 (d, J= 7.2 Hz, 3H) 13C NMR (101 MHz, CDCfi) δ 174.69, 172.32, 162.28, 159.39, 146.57, 141.98, 138.67, 138.59, 137.60, 136.31, 136.01, 129.40, 129.10, 127.95, 127.93, 109.58, 73.40, 57.05, 56.27, 47.89, 33.95, 20.97, 20.94, 19.25, 18.84, 18.04
169 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for CfisHjyBnNjCfi. 663.0341; found, 663.0336 Ή NMR (400 MHz, CDCfi) δ 8.26 (d, J = 5.4 Hz, 1H), 8.21 (d, J= 7.8 Hz, 1H), 7.45 - 7.33 (m, 4H), 7.22 - 7.03 (m, 4H), 6.95 (d, 7=5.4 Hz, 1H), 5.83 - 5.61 (m, 1H), 5.72 (s, 2H), 4.56 (p, J= 7.3 Hz, 1H), 4.01 (d, J= 9.6 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.24 (d, J= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDCfi) δ 172.18, 170.25, 162.91, 160.27, 145.69, 143.97, 142.36, 139.81, 139.71, 131.97, 131.68, 129.87, 129.76, 121.06, 120.77, 109.63, 89.49, 72.51, 56.46, 56.20, 48.06, 20.87, 19.12, 17.81
253
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
170 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C26H31N2O7S2, 547.1572; found, 547.1585 'HNMR (400 MHz, CDC13) δ 8.31 (d, J = 7.9 Hz, 1H), 8.27 (d, J= 5.3 Hz, 1H), 6.94 (d, J= 5.4 Hz, 1H), 6.75 (d, J= 3.4 Hz, 1H), 6.70 - 6.62 (m, 1H), 6.57 - 6.50 (m, 2H), 5.77 - 5.70 (m, 2H), 5.52 - 5.40 (m, 1H), 4.75 - 4.58 (m, 1H), 4.45 (d, J= 7.1Hz, 1H), 3.90 (s, 3H), 2.40 (d,/= 1.2 Hz, 3H), 2.39 (d, J= 1.1 Hz, 3H), 2.06 (s, 3H), 1.36- 1.14 (m, 6H) 13CNMR(101 MHz, CDC13) δ 172.17, 170.25, 162.90, 160.26, 145.69, 143.95, 142.56, 141.64, 140.61, 138.96, 138.93, 125.73, 125.07, 124.65, 124.41, 109.55, 89.54, 74.42, 56.18, 48.23, 47.85, 20.87, 18.66, 18.03, 15.24
171 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O7, 535.2444; found, 535.2449 'Η NMR(400 MHz, CDC13) δ 8.33 8.15 (m, 2H), 7.22 - 7.10 (m, 4H), 7.10 6.99 (m, 4H), 6.92 (d, /= 5.4 Hz, 1H), 5.84 - 5.69 (m, 3H), 4.55 (p, /= 7.3 Hz, 1H), 3.99 (d, /= 10.0 Hz, 1H), 3.87 (s, 3H), 2.27 (s, 3H), 2.24 (s, 3H), 2.05 (s, 3H), 1.24 (d, /= 6.2 Hz, 3H), 0.95 (d, /= 7.2 Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.34, 170.24, 162.87, 160.24, 145.70, 143.90, 142.59, 138.70, 138.58, 136.32, 135.99, 129.40, 129.10, 127.93, 127.90, 109.55, 89.51, 73.38, 57.07, 56.17, 48.12, 20.96, 20.93,20.86, 19.26, 17.81
173 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H28F3N2O6, 545.1899; found, 545.1902 'HNMR (300 MHz, CDC13) δ 8.42 (d, J = 7.7 Hz, 1H), 8.31 (d,/= 5.4 Hz, 1H), 7.60 - 7.50 (m, 2H), 7.47 - 7.37 (m, 2H), 7.34 - 7.13 (m, 5H), 6.99 (d, /= 5.4 Hz, 1H), 5.83 (dq, /= 9.6, 6.2 Hz, 1H), 4.65 - 4.45 (m, 1H), 4.14 (d, /= 9.7 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.25 (d,/= 6.2 Hz, 3H), 0.92 (d, /= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCf) δ -62.56
254
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (A 13c, 19f)
174 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27CI2N2O6, 545.1246; found, 545.1244 'HNMR (300 MHz, CDCfi) δ 8.40 (d, J = 8.1 Hz, 1H), 8.30 (d,7= 5.5 Hz, 1H), 7.31 - 7.12 (m, 8H), 6.99 (d,7= 5.5 Hz, 1H), 5.72 (dq,7=9.5, 6.1Hz, 1H), 4.66 - 4.47 (m, 1H), 4.03 (d, 7= 9.5 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.22 (d,7= 6.1 Hz, 3H), 1.01 (d,7= 7.1 Hz, 3H) 13C NMR (75 MHz, CDCfi) δ 172.06, 168.91, 162.33, 159.45, 146.66, 141.36, 139.32, 139.27, 137.47, 132.94, 132.69, 129.51, 129.41, 129.01, 128.72, 109.85, 72.70, 56.30, 56.27, 47.83, 20.75, 19.09, 17.98
175 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H30F3N2O7, 575.2005; found, 575.2011 'HNMR (300 MHz, CDCfi) δ 8.26 (d, J = 5.4 Hz, 1H), 8.22 (d, 7= 7.8 Hz, 1H), 7.58 - 7.49 (m, 2H), 7.42 (d, 7= 8.2 Hz, 2H), 7.35 - 7.12 (m, 5H), 6.95 (d,7= 5.4 Hz, 1H), 5.84 (dq, 7= 9.8, 6.2 Hz, 1H), 5.72 (s, 2H), 4.62 - 4.48 (m, 1H), 4.15 (d, 7= 9.8 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 0.93 (d,7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCfi) δ -62.57
176 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29CI2N2O7, 575.1352; found, 575.1352 'HNMR (300 MHz, CDCfi) δ 8.26 (d, J = 5.4 Hz, 1H), 8.22 (d, 7= 7.8 Hz, 1H), 7.34 - 7.09 (m, 8H), 6.95 (d, 7= 5.4 Hz, 1H), 5.81 - 5.58 (m, 3H), 4.67 - 4.44 (m, 1H), 4.04 (d, 7= 9.5 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.1 Hz, 3H) 13C NMR (75 MHz, CDCfi) δ 172.19, 170.28, 162.91, 160.27, 145.71, 143.95, 142.32, 139.38, 139.28, 132.94, 132.67, 129.49, 129.40, 129.01, 128.71, 109.64, 89.47, 72.65, 56.32, 56.22, 56.18, 48.05, 20.89, 20.86, 19.12, 17.81
255
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
178 ... (Thin film) 3387, 2984, 1737, 1673, 1603, 1579, 1506, 1451, 1368, 1304, 1268, 1199, 1159, 1136, 1045, 1007, 969, 825, 779, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C27H27F2N2O6, 513.1832; found, 513.1833 'HNMR (400 MHz, CDC13) δ 8.35 (dd, J = 4.5, 1.3 Hz, 1H), 8.15 (d, 7= 7.8 Hz, 1H), 7.52 (dd, J= 8.4, 1.4 Hz, 1H), 7.42 (dd, J= 8.4, 4.5 Hz, 1H), 7.33 - 7.14 (m, 4H), 7.05 - 6.86 (m, 4H), 5.82 (s, 2H), 5.72 (dq,7=9.7, 6.1Hz, 1H), 4.59 (p,7 = 7.3 Hz, 1H), 4.06 (d, J= 9.7 Hz, 1H), 2.11 (s, 3H), 1.24 (d, J= 6.2 Hz, 3H), 1.01 (d, 7=7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -115.57,-115.97
179 ... (Thin film) 3380, 2985, 1737, 1674, 1603, 1578, 1507, 1473, 1455, 1366, 1312, 1274, 1222, 1200, 1158, 1104, 1043, 1003, 968, 910, 886, 824, 792, 728 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O7, 557.2094; found, 557.2089 Ή NMR (400 MHz, CDCf) δ 8.23 (d, J = 5.3 Hz, 1H), 8.18 (d, 7= 7.8 Hz, 1H), 7.23 (ddd, 7= 13.9, 6.9, 2.6 Hz, 4H), 7.05 - 6.84 (m, 5H), 5.78 - 5.66 (m, 3H), 4.56 (p, 7= 7.3 Hz, 1H), 4.12 (q, 7= 7.0 Hz, 2H), 4.05 (d, 7= 9.7 Hz, 1H), 2.06 (s, 3H), 1.47 (t, 7= 7.0 Hz, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCf) δ -115.60,-115.98
256
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
180 ... (Thin film) 3404, 2983, 1737, 1652, 1602, 1508, 1482, 1453, 1369, 1305, 1222, 1197, 1159, 1137, 1106, 1088, 1049, 1010, 976, 911,828, 792, 759, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C28H28F2NO6, 512.1879; found, 512.1889 'H NMR (400 MHz, CDC13) 5 8.13 (dd, J = 7.9, 1.8 Hz, 1H), 8.06 (d, J= 6.9 Hz, 1H), 7.45 (ddd, 7= 8.5, 7.4, 1.8 Hz, 1H), 7.29 - 7.05 (m, 6H), 7.04 - 6.90 (m, 4H), 5.92 (d, 7= 6.4 Hz, 1H), 5.83 (d, 7= 6.4 Hz, 1H), 5.73 (dq, 7= 9.9, 6.2 Hz, 1H), 4.57 (p, 7=7.1 Hz, 1H), 4.06 (d, 7= 9.7 Hz, 1H), 2.14 (s, 3H), 1.25 (d, 7= 6.0 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -115.62,-116.01
181 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C40H39N2O7, 659.2752; found, 659.2758 Ή NMR (400 MHz, CDC13) δ 8.24 (t, J = 7.7 Hz, 2H), 7.57 - 7.49 (m, 8H), 7.45 - 7.37 (m, 8H), 7.32 (dt, 7= 9.3, 5.8 Hz, 2H), 6.90 (d, 7= 5.4 Hz, 1H), 5.89 (dq, J = 12.4, 6.1 Hz, 1H), 5.71 (s, 2H), 4.58 (p, 7=7.3 Hz, 1H), 4.16 (d, 7= 10.0 Hz, 1H), 3.88 (s, 3H), 2.05 (s, 3H), 1.33 (d, J = 6.1 Hz, 3H), 0.96 (d, 7= 7.2 Hz, 3H) 13CNMR(101 MHz, CDC13) δ 172.38, 170.26, 162.88, 160.23, 145.68, 143.94, 142.52, 140.73, 140.61, 140.52, 140.23, 139.89, 139.63, 128.74, 128.71, 128.55, 127.55, 127.26, 127.17, 126.99, 126.96, 109.50, 89.54, 73.27, 57.25, 56.15, 48.12, 20.87, 19.34, 17.79
257
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
182 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C39H37N2O6, 629.2646; found, 629.2651 'HNMR (400 MHz, CDC13) δ 8.41 (d, J = 5.1 Hz, 1H), 8.29 (d, 7= 5.4 Hz, 1H), 7.57 - 7.47 (m, 8H), 7.41 (dd, 7= 9.3, 6.0 Hz, 8H), 7.32 (dd,7= 12.1, 7.1 Hz, 2H), 6.94 (d, 7= 5.5 Hz, 1H), 5.88 (dq, 7= 12.3, 6.1Hz, 1H), 4.57 (p, 7= 7.2 Hz, 1H), 4.15 (d, 7= 10.0 Hz, 1H), 3.87 (s, 3H),2.38(s, 3H), 1.31 (d, 7= 6.1 Hz, 3H), 0.95 (d,7=7.1Hz, 3H) 13C NMR (101 MHz, CDC13) δ 172.24, 168.91, 162.29, 159.40, 146.63, 141.52, 140.73, 140.62, 140.47, 140.23, 139.88, 139.62, 137.45, 128.75, 128.71, 128.56, 127.54, 127.25, 127.16, 127.00, 126.96, 109.69, 73.30, 57.22, 56.25, 47.90, 20.75, 19.31, 17.97
183 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27F2N2O7, 530.1813; found, 530.1809 'HNMR (500 MHz, CDC13) δ 8.28 (d, J = 5.4 Hz, 1H), 8.15 (t,7=5.6 Hz, 1H), 7.25 - 7.15 (m, 4H), 7.03 - 6.89 (m, 5H), 5.75-5.66 (m, 3H),4.11 (dd,7= 18.3, 5.7 Hz, 1H), 4.04 (d,7=9.1Hz, 1H), 3.92 (s, 3H), 3.89 (dd,7= 18.3, 5.4 Hz, 1H), 2.06 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 170.32, 169.11, 161.72 (d, 7= 246.0 Hz), 161.62 (d, 7 = 245.4 Hz), 160.31, 145.73, 144.02, 142.27, 136.67 (d, 7= 26.2 Hz), 129.72, 129.66, 115.68 (d, 7= 21.5 Hz), 115.41 (d, 7= 22.1 Hz), 109.65, 89.48, 73.37,56.16, 55.69,41.33,20.87 19F NMR (471 MHz, CDC13) δ -115.60 (m),-115.94 (m)
258
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
184 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H3T2N2O7, 558.2121; found, 558.2133 'HNMR (500 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 8.22 (d, J= 8.4 Hz, 1H), 7.28 - 7.18 (m, 4H), 7.01 - 6.90 (m, 5H), 5.77 - 5.65 (m, 3H), 4.56 (ddd, 7= 8.4, 6.7, 5.3 Hz, 1H), 4.05 (d,7= 9.6 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.63 - 1.52 (m, 1H), 1.40- 1.29 (m, 1H), 1.23 (d,7=6.2 Hz, 3H), 0.61 (t, 7= 7.4 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.56, 170.27, 163.06, 161.72 (d, 7= 246.0 Hz), 161.66 (d, 7= 245.2 Hz), 160.32, 145.66, 144.03, 142.38, 136.92, 129.60 (d,7= 10.6 Hz), 129.54 (d,7= 10.4 Hz), 115.63 (d, 7= 35.4 Hz), 115.46 (d, 7= 35.4 Hz), 109.55, 89.59, 73.22, 56.19, 56.02, 53.26, 25.24, 20.87, 19.22,9.16 19F NMR (471 MHz, CDC13) δ -115.59--115.70 (m),-116.06 (ddd, 7= 14.0, 8.7, 5.3 Hz)
185 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O7, 572.2283; found, 572.2286 'H NMR (500 MHz, CDC13) δ 8.29 8.21 (m, 2H), 7.29 - 7.14 (m, 4H), 7.00 6.88 (m, 5H), 5.85-5.51 (m, 3H), 4.55 (dd, 7= 9.3, 4.6 Hz, 1H), 4.05 (d, 7= 9.6 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.87 1.75 (m, 1H), 1.22 (d, 7= 6.2 Hz, 3H), 0.78 (d, 7= 6.9 Hz, 3H), 0.58 (d, 7= 6.8 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.17, 170.27, 163.21, 161.70 (d, 7= 246.1 Hz), 161.66 (d, 7= 245.3 Hz), 160.38, 145.62, 144.11, 142.32, 136.98, 129.54, 129.54 (d, 7= 14.9 Hz), 115.63 (d, 7= 32.3 Hz), 115.46 (d, 7= 32.3 Hz), 109.54, 89.63, 73.25, 57.14, 56.19, 55.97, 31.09, 20.88, 19.27, 19.10, 17.06 19F NMR (471 MHz, CDC13) δ -115.69 (ddd, 7= 13.8, 8.8, 5.5 Hz), -116.12 (ddd, 7= 13.8, 8.7, 5.5 Hz)
259
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
186 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C31H35F2N2O7, 585.2407; found, 585.2409 'HNMR (500 MHz, CDC13) δ 8.25 (d, J = 5.4 Hz, 1H), 8.07 (d, J= 8.8 Hz, 1H), 7.28 - 7.18 (m, 4H), 7.01 - 6.91 (m, 5H), 5.74 - 5.66 (m, 3H), 4.57 (ddd, J= 9.6, 8.7, 5.1Hz, 1H), 4.04 (d, 7= 9.9 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.41 - 1.31 (m, 1H), 1.23 (d,7= 6.1 Hz, 3H), 1.22 - 1.17 (m, 1H), 1.04 - 0.96 (m, 1H), 0.79 (d, 7= 6.5 Hz, 3H), 0.74 (d, 7= 6.6 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.38, 170.29, 163.06, 161.73 (d,7= 245.7 Hz), 161.67 (d, 7= 245.4 Hz), 160.35, 145.57, 144.14, 142.22, 137.17, 136.90, 129.57 (d,7= 12.1 Hz), 129.50 (d, 7= 11.8 Hz), 115.64 (d,7= 35.1 Hz), 115.47 (d,7= 35.0 Hz), 109.55, 89.60, 73.08, 56.20, 56.19, 50.69, 41.20, 24.56, 22.80, 21.63, 20.87, 19.19 19F NMR (471 MHz, CDC13) δ -115.66 (td, 7= 9.1, 4.7 Hz), -116.21 (ddd, 7= 13.9, 8.7, 5.3 Hz)
187 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C26H25F2N2O6, 499.1675; found, 499.1664 Ή NMR (500 MHz, CDC13) δ 8.38 8.23 (m, 2H), 7.27 - 7.12 (m, 4H), 7.10 6.83 (m, 5H), 5.69 (dq,7= 9.1, 6.2 Hz, 1H), 4.13 - 3.95 (m, 2H), 3.92 (s, 4H), 2.39 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 168.98, 168.92, 162.91, 161.71 (d, 7= 245.8 Hz), 161.62 (d, 7= 245.4 Hz), 159.51, 146.67, 141.23, 137.55, 136.79, 136.53 (d,7= 3.4 Hz), 129.72 (d, 7= 2.9 Hz), 129.65 (d, 7= 2.7 Hz), 115.67 (d, 7= 21.3 Hz), 115.40 (d, 7= 21.3 Hz), 109.89, 73.42, 56.31,55.71,41.17, 20.73, 19.11 19F NMR (471 MHz, CDC13) δ -115.55--115.66 (m),-115.95 (tt, 7= 8.3, 4.0 Hz)
260
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
188 — — HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O6, 527.1988; found, 527.1981 'H NMR (500 MHz, CDC13) δ 8.39 (s, 1H), 8.32 (d, J= 5.5 Hz, 1H), 7.33 - 7.04 (m, 4H), 7.06 - 6.86 (m, 5H), 5.70 (dq, J = 9.4, 6.1Hz, 1H), 4.54 (ddd, J= 8.6, 6.5, 5.4 Hz, 1H), 4.04 (d, J= 9.4 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.62- 1.49 (m, 1H), 1.40- 1.30 (m, 1H), 1.22 (d,7=6.1 Hz, 3H), 0.59 (t, J= 7.4 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.41, 168.90, 162.46, 161.71 (d, J= 245.9 Hz), 161.66 (d, J= 245.4 Hz), 159.46, 146.63, 141.46, 137.48, 136.88, 129.63 (d,7= 7.8 Hz), 129.53 (d, 7= 7.8 Hz), 115.67 (d, 7= 21.3 Hz), 115.40 (d, 7= 21.1 Hz), 109.74, 73.25, 56.30, 55.96, 53.02, 25.34, 20.76, 19.20, 9.04 19F NMR (471 MHz, CDC13) δ -115.62 --115.72 (m),-116.07 (td, 7= 9.3, 8.9, 4.1 Hz).
189 — — HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O6, 541.2145; found, 541.2143 'H NMR (500 MHz, CDC13) δ 8.35 (s, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.35 - 7.16 (m, 4H), 7.08 - 6.80 (m, 5H), 5.70 (dq,7 = 9.5, 6.1 Hz, 1H), 4.51 (dd, 7= 9.5, 4.7 Hz, 1H), 4.04 (d, 7= 9.5 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.89 - 1.68 (m, 1H), 1.21 (d, 7= 6.3 Hz, 3H), 0.76 (d, 7= 6.9 Hz, 3H), 0.58 (d, 7= 6.9 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.01, 168.88, 162.63, 161.69 (d, 7= 245.9 Hz), 161.65 (d, 7= 244.8 Hz), 159.46, 146.61, 141.54, 137.48, 136.97 (d, 7= 3.3 Hz), 136.88 (d, 7= 3.4 Hz), 129.65 (d, 7= 7.9 Hz), 129.52 (d, 7= 8.0 Hz), 115.66 (d, J = 21.3 Hz), 115.41 (d, 7= 21.3 Hz), 109.71, 73.25, 56.95, 56.30, 55.91, 20.77, 19.25, 18.99, 17.09 19F NMR (471 MHz, CDC13) δ -115.67 --115.78 (m),-116.06-116.17 (m)
261
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
190 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O6, 555.2301; found, 555.2292 'H NMR (500 MHz, CDC13) δ 8.30 (d, J = 5.5 Hz, 1H), 8.18 (d, 7= 8.2 Hz, 1H), 7.35 - 7.13 (m, 4H), 7.04 - 6.80 (m, 5H), 5.68 (dq, 7= 9.8, 6.2 Hz, 1H), 4.54 (td, J = 9.2, 5.2 Hz, 1H), 4.03 (d, 7= 9.7 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.20 (dd, 7= 16.3, 6.1 Hz, 4H), 1.04 (ddd,7= 13.9, 8.7, 5.2 Hz, 1H), 0.91 - 0.81 (m, 1H), 0.78 (d, 7= 6.4 Hz, 3H), 0.73 (d, 7= 6.6 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.20, 168.87, 162.46, 161.71 (d, 7= 245.7 Hz), 161.66 (d, 7= 245.4 Hz), 159.46, 146.57, 141.50, 137.48, 137.07 (d, 7= 3.3 Hz), 136.89 (d, 7= 3.3 Hz), 129.60 (d, 7= 8.0 Hz), 129.50 (d, 7= 8.0 Hz), 115.68 (d, J = 21.3 Hz), 115.40 (d, 7= 21.3 Hz), 109.71, 73.08, 56.23, 50.54, 24.54, 22.76, 21.71,20.76, 19.16 19F NMR (471 MHz, CDC13) δ -115.59--115.77 (m),-116.14-116.29 (m)
191 ... (Thin film) 3381, 2937, 1735, 1676, 1492, 1245, 1203, 1042 HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O9, 567.2335; found, 567.2337 'H NMR (300 MHz, CDC13) δ 8.32 8.19 (m, 2H), 7.47 (dd,7= 7.7, 1.8 Hz, 1H), 7.23 (s, 1H), 7.24 - 7.04 (m, 2H), 6.93 (d, 7= 5.5 Hz, 1H), 6.93 - 6.77 (m, 3H), 6.78 (dd, 7= 8.3, 1.2 Hz, 1H), 5.95 (dq, 7= 9.9, 6.2 Hz, 1H), 5.78 - 5.66 (m, 2H), 5.01 (d, 7= 9.8 Hz, 1H), 4.62 - 4.48 (m, 1H), 3.90 (s, 3H), 3.85 (s, 3H), 3.76 (s, 3H), 2.06 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 0.95 (d, 7=7.2 Hz, 3H)
262
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
192 ... (Thin film) 3378, 2938, 1737, 1675, 1583, 1504, 1488, 1202, 1041 HRMS-ESI (m/z) ([M+H]+) calcd for C30H35N2O9, 567.2341; found, 567.2337 'HNMR (300 MHz, CDCfi) δ 8.27 (d, J = 5.4 Hz, 1H), 8.23 (d, J= 7.8 Hz, 1H), 7.26-7.14 (m, 1H), 7.16 (t, J= 7.9 Hz, 1H), 6.93 (d, J= 5.4 Hz, 1H), 6.92 - 6.87 (m, 2H), 6.87 - 6.80 (m, 2H), 6.73 (ddd, J= 8.2, 2.6, 0.9 Hz, 1H), 6.69 (ddd, J= 8.2, 2.6, 0.9 Hz, 1H), 5.79 (dq, J= 9.7, 5.8 Hz, 1H), 5.73 - 5.69 (m, 2H), 4.71 4.44 (m, 1H), 3.99 (d, J= 10.2 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H), 2.06 (s, 3H), 1.25 (d, J= 6.1 Hz, 3H), 0.94 (d, 7= 7.2 Hz, 3H)
193 ... (Thin film) 3378, 2983, 1741, 1672, 1575, 1483, 1201, 1002 HRMS-ESI (m/z) ([M+H]+) calcd for C28H27CI2F2N2O8, 627.1102; found, 627.1107 'HNMR (400 MHz, CDCfi) δ 8.24 (dt, J = 5.4, 1.3 Hz, 1H), 7.99 (d,7=8.1Hz, 1H), 7.81 (t, 7= 8.5 Hz, 1H), 7.36 (t, 7= 8.5 Hz, 1H), 7.19-7.10 (m, 1H),7.O76.98 (m, 1H), 6.99 - 6.86 (m, 3H), 6.14 6.04 (m, 1H), 5.70 (d, 7= 6.4 Hz, 1H), 5.64 (d, 7= 6.4 Hz, 1H), 4.66 (p, 7= 7.2 Hz, 1H), 3.92 (s, 3H), 3.82 (s, 1H), 2.07 (s, 3H), 1.35 (d, 7= 7.2 Hz, 3H), 1.22 (d, 7=6.9 Hz, 3H)
194 ... (Thin film) 3380, 2984, 1738, 1675, 1504, 1201, 1003 HRMS-ESI (m/z) ([M+H]+) calcd for C30H32F2N2O7, 571.2257; found, 571.225 'HNMR (300 MHz, CDCfi) δ 8.27 (d, J = 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 7.15 - 7.02 (m, 2H), 7.00 - 6.84 (m, 5H), 5.76 - 5.63 (m, 3H), 4.66 - 4.49 (m, 1H), 3.97 (d, 7= 9.8 Hz, 1H), 3.91 (s, 3H), 2.20 (d,7= 1.9 Hz, 3H), 2.18 (d, 7= 1.8 Hz, 3H), 2.06 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDCfi) δ -116.63 (t, 7= 9.5 Hz), -117.12 (t, 7= 9.5 Hz)
195 ... (Thin film) 3377, 2983, 1739, 1675, 1501, 1202, 1050 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33CI2N2O7, 603.1657; found, 603.1659 'HNMR (300 MHz, CDCfi) δ 8.27 (d, J = 5.4 Hz, 1H), 8.23 (d, 7= 7.9 Hz, 1H), 7.25 - 7.20 (m, 2H), 7.17 - 7.02 (m, 4H), 6.94 (d, 7= 5.4 Hz, 1H), 5.75 - 5.62 (m, 3H), 4.68 - 4.50 (m, 1H), 3.95 (d, 7= 9.9 Hz, 1H), 3.91 (s, 3H), 2.31 (s, 3H), 2.28 (s, 3 El), 2.06 (s, 3 El), 1.24 (d, 7=6.1 Hz, 3H), 1.03 (d, 7= 7.2 Hz, 3H)
263
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
196 ... (Thin film) 3379, 2987, 1741, 1673, 1507, 1486, 1453, 1203, 1002 HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O8, 559.1884; found, 559.1886 Ή NMR (400 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 8.13 (d, 7= 8.1 Hz, 1H), 7.85 (tt,7=7.6, 1.9 Hz, 1H), 7.47 (tt, 7= 7.7, 1.8 Hz, 1H), 7.28 - 7.20 (m, 1H), 7.22 - 7.11 (m, 2H), 7.09 - 6.99 (m, 1H), 7.01 - 6.79 (m, 3H), 6.29 - 6.20 (m, 1H), 5.71 (d, 7= 6.4 Hz, 1H), 5.67 (d, 7= 6.4 Hz, 1H), 4.75 - 4.57 (m, 1H), 3.91 (s, 3H), 3.48 (d, 7= 6.1 Hz, 1H),2.O7 (s, 3H), 1.34-1.21 (m, 6H)
197 ... (Thin film) 3379, 3282, 2984, 2107, 1738, 1674, 1503, 1202, 1043, 1004 HRMS-ESI (m/z) ([M+H]+) calcd for C32H31N2O7, 555.2125; found, 555.2126 'HNMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.21 (d, 7= 7.8 Hz, 1H), 7.46 - 7.34 (m, 5H), 7.26 - 7.15 (m, 3H), 6.94 (d, 7= 5.4 Hz, 1H), 5.87 - 5.68 (m, 3H), 4.62 - 4.48 (m, 1H), 4.07 (d, 7= 9.8 Hz, 1H), 3.91 (s, 3H), 3.05 (s, 1H), 3.03 (s, 1H), 2.06 (s, 3H), 1.34 - 1.22 (m, 3H), 0.98 (d, 7= 7.2 Hz, 3H)
198 ... (Thin film) 3379, 2964, 1736, 1675, 1505, 1202, 1042, 1003 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O7, 563.2753; found, 563.2752 'HNMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 7.24 - 7.18 (m, 4H), 7.14 - 7.03 (m, 5H), 6.93 (d, 7= 5.5 Hz, 1H), 5.87 - 5.69 (m, 3H), 4.53 (p, 7= 7.3 Hz, 1H), 3.99 (d, 7= 10.1 Hz, 1H), 3.90 (d,7= 1.0 Hz, 3H), 2.68-2.48 (m, 4H), 2.06 (d,7= 1.1 Hz, 3H), 1.24 (d, 7= 7.1 Hz, 3H), 1.22-1.10 (m, 6H), 0.88 (d, 7= 7.2 Hz, 2H)
264
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
199 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O7, 525.2032; found, 525.2045 'HNMR (400 MHz, CDC13) δ 8.27 (d, J = 5.3 Hz, 1H), 8.21 (d, J= 7.9 Hz, 1H), 7.31 - 7.22 (m, 5H), 7.21 - 7.12 (m, 1H), 7.00 - 6.81 (m, 3H), 5.81 - 5.74 (m, 1H), 5.72 (d, J= 0.8 Hz, 2H), 4.54 (p, J= 7.2 Hz, 1H), 4.05 (d, J= 9.9 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.24 (d, J= 6.2 Hz, 3H), 0.92 (d,7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.31, 170.28, 162.87, 161.70 (d, J= 245.6 Hz), 160.25, 145.69, 143.97, 142.50, 141.20, 137.03 (d, J= 3.3 Hz), 129.60 (d, J= 7.8 Hz), 128.59, 128.02, 126.80, 115.60 (d, J = 21.3 Hz), 109.52, 89.55, 73.11, 57.04, 56.18,48.05,20.87, 19.18, 17.74
201 ... ... ESIMS m/z 661.1 ([M+H]+) Ή NMR (400 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 7.89 (d, J= 8.0 Hz, 1H), 7.56 (d, J= 2.2 Hz, 1H), 7.48 (d, J= 2.2 Hz, 1H), 7.34 (dd, J= 8.5, 4.2 Hz, 2H), 7.18 (ddd, J= 10.5,8.4,2.2 Hz, 2H), 6.97 (d, J= 5.4 Hz, 1H), 5.79 (q, J= 6.3 Hz, 1H), 5.68 (d, J= 6.3 Hz, 1H), 5.61 (d, J= 6.4 Hz, 1H), 4.63 - 4.52 (m, 1H), 3.92 (s, 3H), 3.55 (s, 1H), 2.07 (s, 3H), 1.27 (d, 7= 7.2 Hz, 3H), 1.18 (d, 7= 6.3 Hz, 3H) 13C NMR (126 MHz, acetone-Jg) δ 166.30, 165.13, 158.33, 155.10, 140.60, 139.16, 138.49, 137.43, 137.10, 127.58, 126.60, 126.48, 125.21, 123.17, 122.62, 119.99, 119.77, 104.55, 84.15, 73.35, 69.04, 51.05, 43.24, 26.40, 15.69, 9.20
265
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¥, 13C, 19F)
202 ... ... ESIMS m/z 627.1 ([M]+) 'HNMR (400 MHz, CDCf) δ 8.26 (d, J = 5.4 Hz, 1H), 7.91 (d, J= 8.0 Hz, 1H), 7.33 - 7.27 (m, 3H), 7.21 (dd, J= 10.4, 2.1Hz, 1H), 7.11 (ddd, J= 8.5, 2.2, 0.8 Hz, 1H), 7.06 (ddd, 7= 8.6, 2.1, 0.9 Hz, 1H), 6.97 (d, J= 5.4 Hz, 1H), 5.80 (q, J= 6.3 Hz, 1H), 5.68 (d, J= 6.3 Hz, 1H), 5.61 (d, 7= 6.3 Hz, 1H), 4.63 - 4.51 (m, 1H), 3.92 (s, 3H), 3.54 (s, 1H), 2.07 (s, 3H), 1.25 (d, 7= 7.2 Hz, 3H), 1.18 (d, 7= 6.4 Hz, 3H) 13C NMR (126 MHz, CDCf) δ 171.43, 170.32, 163.50, 160.30, 157.99 (d,7= 249.5 Hz), 157.96 (d, 7= 249.3 Hz), 145.76, 145.20 (d, 7= 5.8 Hz), 143.73, 143.09 (d, 7=6.1 Hz), 142.58, 130.53 (d, 7= 3.2 Hz), 122.14 (d,7= 3.8 Hz), 121.85 (d, 7= 3.5 Hz), 120.23 (d,7= 17.8 Hz), 120.05 (d, 7= 17.8 Hz), 114.70 (d, 7= 22.5 Hz), 114.34 (d, 7= 23.0 Hz), 109.72, 89.34, 78.60, 74.30, 56.24, 48.39, 30.94, 20.86, 17.51, 14.43
203 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33CI2N2O7, 603.1659; found, 603.1666 'HNMR (400 MHz, CDCf) δ 8.27 (d, J = 5.4 Hz, 1H), 8.21 (d, 7= 7.8 Hz, 1H), 7.26 - 7.19 (m, 2H), 7.10 (dd, 7= 8.5, 2.2 Hz, 2H), 7.03 (ddd,7= 13.4, 8.2, 2.3 Hz, 2H), 6.94 (d, 7= 5.5 Hz, 1H), 5.77 - 5.62 (m, 3H), 4.56 (p, 7= 7.2 Hz, 1H), 3.95 (d, 7= 10.0 Hz, 1H), 3.91 (s, 3H), 2.33 (s, 3H), 2.31 (s, 3H), 2.06 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDCf) δ 172.30, 170.28, 162.90, 160.27, 145.70, 143.97, 142.42, 139.64, 139.47, 136.51, 136.11, 133.06, 132.71, 130.74, 130.63, 129.42, 129.12, 126.63, 126.49, 109.57, 89.52, 72.78, 56.44, 56.19, 48.06, 20.87, 20.17, 20.09, 19.19 17.82
266
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
204 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H27FN2O6, 495.1926; found, 495.1920 'HNMR (400 MHz, CDC13) δ 8.40 (d, J = 7.9 Hz, 1H), 8.32 (d, J= 5.5 Hz, 1H), 7.30 - 7.22 (m, 6H), 7.19 - 7.13 (m, 1H), 7.01 - 6.93 (m, 3H), 5.76 (dq, J= 9.8, 6.2 Hz, 1H), 4.58 - 4.49 (m, 1H), 4.05 (d, J= 9.9 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.23 (d, J= 6.1 Hz, 3H), 0.90 (d, J= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.19, 168.90, 162.27, 161.69 (d, J= 245.6 Hz), 159.42, 146.64, 141.51, 141.14, 137.46, 137.02 (d, J= 3.2 Hz), 129.60 (d, J= 7.8 Hz), 128.59, 128.04, 126.81, 115.59 (d, J = 21.2 Hz), 109.72, 73.14, 56.99, 56.28, 47.81,20.74, 19.15, 17.92
206 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H31CI2N2O6, 573.1554; found, 573.1551 'H NMR (400 MHz, CDC13) δ 8.40 (s, 1H), 8.32 (d, J= 5.4 Hz, 1H), 7.22 (dd, J = 17.1, 8.2 Hz, 2H), 7.09 (dd, J=12, 2.2 Hz, 2H), 7.06 - 6.96 (m, 3H), 5.69 (dq, J = 9.9, 6.2 Hz, 1H), 4.61 - 4.47 (m, 1H), 3.96 - 3.92 (m, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.30 (s, 3H), 1.22 (d, J = 6.2 Hz, 3H), 0.99 (d, J= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.16, 168.91, 162.30, 159.45, 146.64, 141.45, 139.58, 137.47, 136.50, 136.10, 133.05, 132.71, 130.73, 130.63, 129.41, 129.12, 126.64, 126.51, 109.76, 72.82, 56.34, 47.83,20.75,20.16, 20.09, 19.16, 18.00
267
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
207 52- 65 ... HRMS-FAB (m/z) ([M+H]+) calcd for C30H33F2N2O6, 555.2301; found, 555.2311 'H NMR (500 MHz, CDC13) δ 8.30 (d, J = 5.5 Hz, 1H), 8.29 (br s, 1H), 7.26 7.18 (m, 4H), 7.01 - 6.88 (m, 5H), 5.70 (dq, J= 9.5, 6.1 Hz, 1H), 4.64 - 4.48 (m, 1H), 4.04 (d, J= 9.5 Hz, 1H), 3.88 (s, 3H), 1.39 (s, 9H), 1.22 (d, 7=6.1 Hz, 3H), 0.99 (d,7=7.1Hz, 3H) 13C NMR (126 MHz, CDC13) δ 176.0, 172.3, 162.2, 161.7 (d, 7= 245.8 Hz), 161.6 (d, 7 = 245.6 Hz), 159.4, 146.5, 142.1, 137.8, 136.9, 136.8, 129.6 (d, 7= 8.0 Hz), 129.5 (d, 7= 7.8 Hz), 115.7 (d, 7 = 21.3 Hz), 115.4 (d,7=21.3 Hz), 109.5, 73.0, 56.3, 56.1, 47.8, 39.1, 27.2, 19.1, 18.1 19F NMR (471 MHz, CDC13) δ -115.7,-116.0
208 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O6, 541.2145; found, 541.2159 Ή NMR (400 MHz, CDC13) δ 8.30 (d, J = 5.4 Hz, 2H), 7.28 - 7.14 (m, 4H), 7.02 - 6.89 (m, 5H), 5.70 (dq, 7= 9.5, 6.2 Hz, 1H), 4.63 - 4.48 (m, 1H), 4.04 (d, 7= 9.5 Hz, 1H), 3.87 (s, 3H), 2.93 (hept, 7= 7.0 Hz, 1H), 1.34 (d, 7= 7.0 Hz, 6H), 1.22 (d, 7= 6.2 Hz, 3H), 0.98 (d, 7= 7.1 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 174.69, 172.21, 162.69, 162.61, 162.28, 160.74, 160.66, 159.43, 146.54, 141.81, 137.65, 136.86, 136.84, 129.64, 129.57, 129.51, 115.76, 115.59, 115.46, 115.30, 109.61, 73.03, 56.29, 56.07, 47.79, 33.94, 19.12, 18.80, 18.04
268
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
209 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O7, 557.209; found, 557.2094 'HNMR (400 MHz, CDCfi) δ 8.45 8.25 (m, 2H), 7.30 - 7.15 (m, 4H), 7.05 6.86 (m, 5H), 5.71 (dtd, 7= 9.7, 7.3, 6.8, 5.5 Hz, 1H), 4.53 (tt, 7= 8.3, 6.6 Hz, 1H), 4.04 (d, 7= 9.6 Hz, 1H), 3.88 (d, 7= 1.2 Hz, 3H), 3.80 (td, 7= 6.6, 1.2 Hz, 2H), 3.39 (d, 7= 1.2 Hz, 3H), 2.97 (td, 7 = 6.7, 1.3 Hz, 2H), 1.22 (dd,7=6.3,1.3 Hz, 3H), 0.98 (dd, 7= 7.2, 1.3 Hz, 3H) 13C NMR (126 MHz, CDCfi) δ 172.13, 169.42, 162.70, 162.61, 162.25, 160.74, 160.66, 159.46, 146.69, 141.44, 137.34, 136.87, 136.84, 136.81, 129.63, 129.56, 129.50, 115.77, 115.60, 115.47, 115.30, 109.78, 73.06, 67.57, 58.76, 56.31, 56.08, 47.81,34.62, 19.12, 17.99
210 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C29H29F2N2O6, 539.1985; found, 539.1988 'HNMR (400 MHz, CDCfi) δ 8.33 (dd, J = 19.6, 5.4 Hz, 2H), 7.25 - 7.16 (m, 4H), 7.03 - 6.88 (m, 5H), 5.70 (dq, 7= 9.5, 6.2 Hz, 1H), 4.65 - 4.52 (m, 1H), 4.04 (d, 7= 9.6 Hz, 1H), 3.90 (s, 3H), 1.95 (tt,7= 8.0,4.6 Hz, 1H), 1.25 (dd, 7= 4.6, 3.1 Hz, 2H), 1.22 (d, 7= 6.2 Hz, 3H), 1.05 (dt, 7= 8.1, 3.5 Hz, 2H), 0.98 (d,7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDCfi) δ 172.45, 172.20, 162.70, 162.61, 162.26, 160.74, 160.66, 159.50, 146.56, 141.80, 137.45, 136.87, 136.85, 136.83, 129.64, 129.57, 129.50, 115.76, 115.59, 115.47, 115.30, 109.68, 73.03, 56.31, 56.08, 47.75, 19.13, 18.09, 13.00, 9.27
269
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
211 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O7, 571.2242; found, 571.225 'HNMR (400 MHz, CDCf) δ 8.25 (t, J = 6.2 Hz, 2H), 7.32 - 7.11 (m, 4H), 7.04 - 6.85 (m, 5H), 5.79 - 5.65 (m, 3H), 4.55 (p, J= 7.3 Hz, 1H), 4.04 (d, J= 9.7 Hz, 1H), 3.87 (s, 3H), 2.53 (hept, J= 7.0 Hz, 1H), 1.23 (d, 7= 6.2 Hz, 3H), 1.12 (d, 7= 7.0 Hz, 6H), 0.99 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 176.25, 172.25, 162.88, 162.70, 162.60, 160.74, 160.65, 160.26, 145.54, 144.21, 142.02, 136.94, 136.92, 136.86, 136.83, 129.60, 129.56, 129.54, 129.49, 115.77, 115.60, 115.47, 115.30, 109.53, 89.88, 73.01, 56.13, 48.05, 33.85, 19.15, 18.66, 17.81
212 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O8, 587.2199; found, 587.2217 'HNMR (400 MHz, CDC13) δ 8.23 (dd, J = 16.1, 6.6 Hz, 2H), 7.25 - 7.18 (m, 4H), 7.02 - 6.89 (m, 5H), 5.82 - 5.66 (m, 3H), 4.54 (p, 7= 7.3 Hz, 1H), 4.08 (s, 2H), 4.04 (d, 7= 9.7 Hz, 1H), 3.89 (s, 3H), 3.58 (q, 7= 7.0 Hz, 2H), 1.25- 1.20 (m, 6H), 0.99 (d,7=7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.20, 170.05, 162.84, 162.70, 162.61, 160.75, 160.65, 160.21, 145.73, 143.95, 142.23, 136.95, 136.92, 136.85, 136.83, 129.60, 129.56, 129.54, 129.50, 115.78, 115.61, 115.47, 115.30, 109.70, 89.55, 73.04, 67.78, 67.17, 56.23, 56.14, 53.46, 48.04, 19.15, 17.81, 15.00, 14.95
270
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
213 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O6, 555.2301; found, 555.2315 'HNMR (400 MHz, CDC13) δ 8.45 8.22 (m, 2H), 7.30 - 7.15 (m, 4H), 7.04 6.89 (m, 5H), 5.71 (dq, 7= 9.5, 6.2 Hz, 1H), 4.63 - 4.45 (m, 1H), 4.04 (d, 7= 9.6 Hz, 1H), 3.89 (s, 3H), 2.68 (t, 7= 7.6 Hz, 2H), 1.76 (p, 7= 7.6 Hz, 2H), 1.54-1.37 (m, 2H), 1.22 (d, 7= 6.1 Hz, 3H), 1.06 0.88 (m, 6H) 13C NMR (126 MHz, CDC13) δ 172.17, 171.61, 162.70, 162.61, 162.31, 160.74, 160.66, 159.47, 146.56, 141.61, 137.57, 136.87, 136.85, 136.82, 129.63, 129.57, 129.50, 115.76, 115.60, 115.47, 115.30, 109.69, 73.05, 56.26, 56.08, 47.80, 33.64, 29.70, 26.61,22.20, 19.12, 18.02, 13.76
214 ... (Thin film) 3388, 2970, 2363, 2029, 1738, 1677, 1604, 1508, 1449, 1414, 1366, 1307, 1218, 1203, 1159, 1139, 1113, 1042, 1000, 970, 908, 831, 806, 793, 778,731, 711,682, 670, 663 HRMS-ESI (m/z) ([M+H]+) calcd for 593.0921; found, 593.0925 'HNMR (400 MHz, CDC13) δ 8.28 (d, J = 7.8 Hz, 1H), 8.17 (d, 7= 4.9 Hz, 1H), 7.68 (d, 7= 4.9 Hz, 1H), 7.30 - 7.16 (m, 4H), 7.05 - 6.90 (m, 3H), 5.81 - 5.69 (m, 3H), 4.54 (p, 7= 7.3 Hz, 1H), 4.05 (d, 7= 9.8 Hz, 1H), 2.09 (s, 3H), 1.59 (s, 1H), 1.31-1.21 (m, 3H), 1.00 (d, 7= 7.2 Hz, 3H)
271
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
215 ... (Thin film) 3380, 2985, 2362, 1769, 1738, 1674, 1609, 1591, 1572, 1513, 1434, 1367, 1310, 1277, 1202, 1175, 1150, 1113, 1051, 1009, 952, 907,825, 805,731, 668, 657 HRMS-ESI (m/z) ([M+H]+) calcd for C27H25F4N2O6, 549.1643; found, 549.1655 'H NMR (300 MHz, CDCf) δ 8.38 (d, J = 8.0 Hz, 1H), 8.32 (d, J= 5.4 Hz, 1H), 7.18 - 6.88 (m, 7H), 5.64 (dq, J= 9.5, 6.3 Hz, 1H), 4.64 - 4.47 (m, 1H), 4.00 (d, J= 9.3 Hz, 1H), 3.91 (s, 3H), 2.39 (s, 3H), 1.23 (d,7=6.1Hz, 3H), 1.09 (d,7=7.2 Hz, 3H) 19FNMR(471 MHz, CDCf) δ -136.31 (ddd,7=20.1, 11.2,8.2 Hz),-136.74 (ddd, 7= 20.3, 11.3, 7.8 Hz), -139.14 - 139.50 (m), -139.70 (dddd,7= 21.4, 10.6, 7.7, 4.1 Hz)
272
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
216 ... (Thin film) 3375, 2984, 2361, 2132, 1770, 1738, 1676, 1590, 1572, 1499, 1452, 1437, 1367, 1311, 1251, 1199, 1175, 1098, 1061, 1010, 952, 907, 828, 805, 782, 764,733, 687, 668, 657, 651 HRMS-ESI (m/z) ([M+H]+) calcd for C27EI25CI2F2N2O6, 581.1052; found, 581.1061 'H NMR (300 MHz, CDCf) δ 8.38 (d,/ = 8.3 Hz, 1H), 8.31 (d,/= 5.4 Hz, 1H), 7.26 (ddd,/= 11.5, 7.2, 2.1 Hz, 2H), 7.18 - 6.95 (m, 5H), 5.63 (dq, J= 9.3, 6.1 Hz, 1H), 4.65 - 4.49 (m, 1H), 4.00 (d, J= 9.4 Hz, 1H), 3.91 (s, 3H), 2.39 (s, 3H), 1.24 (d,/= 6.2 Hz, 3H), 1.09 (d,/= 7.2 Hz, 3H) 19FNMR(471 MHz, CDCf) δ -116.85 -117.26 (m), -117.29 - -117.50 (m)
273
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
217 ... (Thin film) 3383, 2983, 1771, 1736, 1676, 1591, 1572, 1503, 1451, 1437, 1366, 1311, 1277, 1237, 1201, 1176, 1119, 1099, 1051, 1009, 949, 907,825, 805, 790, 733, 668, 657 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O6, 541.2145; found, 541.2156 'HNMR (300 MHz, CDC13) δ 8.40 (d, J = 8.2 Hz, 1H), 8.32 (d, J= 5.4 Hz, 1H), 7.14-6.96 (m, 5H), 6.96-6.81 (m, 2H), 5.68 (dq, J= 9.9, 6.1 Hz, 1H), 4.53 (dt, J = 8.2, 7.1Hz, 1H), 3.94 (d,7= 10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.22 (dd, J= 6.7, 1.9 Hz, 6H), 1.21 (d, J= 6.1 Hz, 3H), 0.98 (d, 7= 7.1 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -119.90 - -120.14 (m), -120.50 -120.65 (m)
274
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
218 ... (Thin film) 3376, 2988, 2363, 1742, 1675, 1609, 1580, 1515, 1454, 1435, 1368, 1310, 1284, 1236, 1203, 1181, 1149, 1120, 1043, 1004, 970, 910,873, 829, 754, 734 HRMS-ESI (m/z) ([M+H]+) calcd for C28H27F4N2O7, 579.1749; found, 579.1762 'HNMR (300 MHz, CDCE) δ 8.27 (d, J = 5.4 Hz, 1H), 8.21 (d, J= 7.8 Hz, 1H), 7.18 - 6.85 (m, 7H), 5.72 (s, 2H), 5.65 (dq,7= 10.5, 6.2 Hz, 1H), 4.58 (p, 7= 7.3 Hz, 1H), 4.01 (d, 7= 9.4 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.25 (d,7= 5.9 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -136.29 (ddd, 7= 20.1, 11.2, 8.0 Hz), 136.73 (ddd, 7= 20.1, 11.3,8.0 Hz), 139.16--139.43 (m),-139.64-139.84 (m)
275
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (A 13c, 19f)
219 ... (Thin film) 3393, 2986, 2364, 1742, 1676, 1580, 1499, 1454, 1437, 1408, 1367, 1310, 1250, 1202, 1180, 1148, 1101, 1061, 1044, 1004, 972, 911,829, 732, 720, 687 HRMS-ESI (m/z) ([M+H]+) calcd for C28H27CI2F2N2O7, 611.1158; found, 611.1169 'HNMR (300 MHz, CDCfi) δ 8.27 (dd, J = 5.4, 1.1 Hz, 1H), 8.21 (d, 7= 7.8 Hz, 1H), 7.35 - 7.19 (m,2H), 7.20-7.01 (m, 4H), 6.96 (dd,7=5.5, 1.1 Hz, 1H), 5.72 (d,7= 1.1 Hz, 2H), 5.64 (dddd,7= 11.6, 9.1, 5.3, 3.3 Hz, 1H), 4.65 - 4.51 (m, 1H), 4.01 (d, 7= 9.5 Hz, 1H), 3.92 (d, 7= 1.1 Hz, 3H), 2.07 (d,7= 1.1 Hz, 3H), 1.30-1.21 (m, 3H), 1.09 (dd, 7= 7.1, 1.1 Hz, 3H) 19F NMR (471 MHz, CDCfi) δ -116.92--117.10 (m),-117.36-117.53 (m)
276
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
220 ... (Thin film) 3375, 2986, 1738, 1675, 1579, 1501, 1452, 1437, 1366, 1310, 1275, 1237, 1202, 1180, 1151, 1118, 1101, 1043, 1003, 970, 909, 828, 785, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O7, 571.2250; found, 571.2265 'HNMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.21 (d, J= 7.8 Hz, 1H), 7.05 (td, J= 9.7, 8.2, 4.2 Hz, 4H), 6.98 6.82 (m, 3H), 5.78 - 5.54 (m, 3H), 4.63 4.48 (m, 1H), 3.95 (d,7= 10.1 Hz, 1H), 3.91 (s, 3H), 2.22 (dd,7= 6.4, 2.0 Hz, 6H), 2.06 (s, 3H), 1.23 (d,7=6.1 Hz, 3H), 0.99 (d,7=7.2 Hz, 3H) 19F NMR (471 MHz, CDC13) δ -120.03 (dt, 7= 9.7, 5.9 Hz), -120.57 (dd, 7=8.8,5.4 Hz)
221 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H27CI4N2O7, 643.0567; found, 643.0578 Ή NMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.20 (d, 7= 7.8 Hz, 1H), 7.42 - 7.29 (m, 4H), 7.12 (dd, 7= 8.3, 2.2 Hz, 1H), 7.08 (dd, 7= 8.3, 2.2 Hz, 1H), 6.95 (d, 7= 5.4 Hz, 1H), 5.72 (s, 2H), 5.70-5.58 (m, 1H), 4.58 (p,7= 7.2 Hz, 1H), 4.00 (d, 7= 9.5 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.13, 170.29, 162.96, 160.28, 145.71, 144.01, 142.25, 140.34, 133.06, 132.72, 131.62, 131.29, 130.94, 130.67, 130.34, 130.11, 127.32, 109.64, 89.50, 72.10, 56.20, 55.71,48.07, 20.88, 19.07, 17.85
277
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
222 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H27CI2F2N2O7, 611.1158; found, 611.1175 'HNMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.20 (d, J= 7.8 Hz, 1H), 7.32 (td, J= 8.3, 7.6 Hz, 2H), 7.11 - 6.93 (m, 4H), 5.72 (d, J= 0.5 Hz, 3H), 5.71 5.60 (m, 1H), 4.67 - 4.51 (m, 1H), 4.03 (d, J= 9.3 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.26 (d, J= 6.2 Hz, 3H), 1.09 (d, J= 7.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 172.10, 170.29, 162.95, 160.29, 158.15 (d,7= 250.2 Hz), 158.01 (d, J= 249.8 Hz), 145.70, 144.03, 142.24, 141.03 (d,7= 6.5 Hz), 131.08, 130.80, 124.51 (d,7= 3.5 Hz), 124.40 (d, J= 3.6 Hz), 120.03 (d, 7= 17.6 Hz), 119.73 (d,7= 17.7 Hz), 116.55 (d,7=21.8 Hz), 109.64, 89.51, 72.15, 56.20, 55.99, 48.05, 20.87, 19.03, 17.84
223 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H25CI4N2O6, 613.0461; found, 613.0468 Ή NMR (300 MHz, CDC13) δ 8.80 (d,7 = 6.6 Hz, 1H), 8.49 (d, 7= 6.8 Hz, 1H), 7.58 (d, 7= 6.6 Hz, 1H), 7.40 - 7.27 (m, 4H), 7.14-7.01 (m, 2H), 5.67-5.52 (m, 1H), 4.61- 4.46 (m, lH),4.18(s, 3H), 4.10 (d, 7= 9.9 Hz, 1H), 2.44 (s, 3H), 1.27 (dd,7= 6.3, 3.1Hz, 6H) 13C NMR (126 MHz, CDC13) δ 174.00, 171.63, 170.13, 140.79, 140.20, 133.07, 132.34, 131.62, 130.97, 130.85, 130.55, 130.04, 127.30, 126.71, 108.57, 72.40, 58.02,55.48, 34.67, 18.65, 16.34
278
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
224 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C27H25CI2F2N2O6, 581.1052; found, 581.1059 'H NMR (300 MHz, CDC13) δ 8.88 (d, J = 6.7 Hz, 1H), 8.49 (d, J= 6.7 Hz, 1H), 7.67 (d, J= 6.7 Hz, 1H), 7.38 - 7.28 (m, 2H), 7.09 - 6.95 (m, 4H), 5.68 - 5.49 (m, 1H), 4.59 - 4.48 (m, 1H), 4.21 (s, 3H), 4.12 (d, 7=9.8 Hz, 1H), 2.44 (s, 3H), 1.31- 1.24 (m, 6H) 13C NMR (126 MHz, CDC13) δ 174.30, 171.60, 170.11, 157.88 (d, 7= 307.7 Hz), 141.43 (d, 7= 6.1 Hz), 140.87 (d, 7= 6.2 Hz), 131.11, 130.71, 124.43, 123.96 (d, 7 = 3.6 Hz), 120.02 (d, 7= 17.7 Hz), 119.27 (d, 7= 17.3 Hz), 116.85 (d, 7= 21.3 Hz), 116.32 (d, 7= 21.5 Hz), 108.58, 72.61, 58.04, 55.77, 50.35, 31.59, 18.66, 16.35 19F NMR (471 MHz, CDC13) δ -113.83 - -113.93 (m), -114.77 (t, 7= 8.7 Hz)
225 ... ... HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1937; found, 543.1949 'HNMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.13 (d, 7= 7.8 Hz, 1H), 7.25 - 7.14 (m, 4H), 6.93 (dddd, 7= 18.3, 8.7, 6.6, 2.1 Hz, 5H), 5.75 - 5.61 (m, 3H), 4.64 - 4.42 (m, 1H), 4.05 (d, 7= 8.9 Hz, 1H), 3.91 (s, 3H), 2.05 (s, 3H), 1.31 (d, 7 =7.1 Hz, 3H), 1.21 (d, 7= 6.2 Hz, 3H) 13C NMR (126 MHz, CDC13) δ 171.93, 170.30, 162.76, 162.66, 160.62, 160.36, 145.64, 144.15, 142.26, 136.92, 136.54, 129.80, 129.74, 129.69, 129.62, 115.71, 115.54, 115.42, 115.25, 109.59, 89.62, 73.10, 56.21, 55.59, 48.03, 20.86, 18.95, 18.06
279
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
226 — (Thin film) 3375, 2982, 1704, 1623, 1527, 1448, 1367, 1346, 1239, 1215, 1165, 1117, 1094, 1043,863, 803,786, 729, 679 HRMS-ESI (m/z) [M+Na]+ calcd for C23H23F6NNaO4, 514.1423; found, 514.1428 Ή NMR (400 MHz, CDC13) δ 6.95 6.77 (m, 4H), 5.57 (dq, J= 9.0, 6.2 Hz, 1H), 4.91 (d, 7= 7.8 Hz, 1H), 4.27 - 4.13 (m, 1H), 3.93 (d, 7= 9.0 Hz, 1H), 1.42 (s, 9H), 1.24 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -132.38 (d, 7= 20.6 Hz), -132.83 (d,7= 20.6 Hz), -160.90 (t, 7= 20.5 Hz), -161.25 (t, 7= 20.6 Hz)
227 — (Thin film) 2939, 2031, 1744, 1620, 1526, 1447, 1345, 1234, 1217, 1118, 1041, 1005, 872, 826, 802, 752, 729, 707, 680, 666, 659 HRMS-ESI (m/z) ([M+H]+) calcd for C18H16F6NO2, 392.1080; found, 392.1083 1H NMR (400 MHz, methanol-74) δ 7.36 - 7.17 (m, 4H), 5.83 (dq,7= 10.0, 6.1 Hz, 1H), 4.26 (d, 7= 10.1 Hz, 1H), 4.00 (q, 7= 7.2 Hz, 1H),3.31 (p,7= 1.7 Hz, 3H), 1.28 (d, 7= 6.2 Hz, 3H), 1.08 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, methanol-74) δ -137.08 (d, 7= 20.0 Hz), -137.39 (d, 7= 19.9 Hz), -166.29 (t, 7= 19.9 Hz), -166.61 (t,7= 19.9 Hz)
280
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
228 ... (Thin film) 3373, 2942, 1738, 1649, 1622, 1577, 1525, 1481, 1446, 1344, 1262, 1239, 1214, 1148, 1117, 1094, 1040, 984, 954, 909, 849, 801, 727, 678 HRMS-ESI (m/z) ([M+H]+) calcd for C25H21F6N2O5, 543.1349; found, 543.1362 'H NMR (400 MHz, CDC13) δ 11.93 (s, 1H), 8.29 (d, J= 7.9 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 6.94 - 6.77 (m, 5H), 5.58 (dq, 7= 9.0, 6.2 Hz, 1H), 4.65 - 4.49 (m, 1H), 3.94 (d,7= 5.5 Hz, 4H), 1.25 (dd,7 = 9.4, 6.7 Hz, 6H) 19F NMR (376 MHz, CDC13) δ -132.34 (d, 7= 20.7 Hz), -132.74 (d, 7= 20.5 Hz), -160.82 (t, 7= 20.5 Hz), -161.08 (t, 7= 20.5 Hz)
281
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13c, 19f)
229 ... (Thin film) 3384, 2985, 1770, 1741, 1676, 1622, 1592, 1572, 1527, 1447, 1368, 1345, 1312, 1237, 1199, 1176, 1117, 1095, 1042, 1010, 954, 909, 846, 828,803, 729, 680 HRMS-ESI (m/z) ([M+H]+) calcd for C27H23F6N2O6, 585.1455; found, 585.1464 'HNMR (400 MHz, CDCf) δ 8.37 (d, J = 7.6 Hz, 1H), 8.32 (d, J= 5.4 Hz, 1H), 7.01 (d, J= 5.5 Hz, 1H), 6.88 (dd, J= 8.1, 6.3 Hz, 2H), 6.82 (dd, 7= 8.1, 6.2 Hz, 2H), 5.56 (dq, 7= 8.7, 6.2 Hz, 1H), 4.65-4.50 (m, 1H), 3.94 (d, 7= 8.8 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.24 (d, J = 6.2 Hz, 3H), 1.18 (d, 7= 7.2 Hz, 3H) 19F NMR (376 MHz, CDCf) δ -132.51 (d, 7= 20.5 Hz), -132.94 (d, 7= 20.4 Hz), -161.06 (t, 7= 20.5 Hz), -161.30 (t, 7= 20.6 Hz)
282
2019201931 20 Mar 2019
Cmpd. No. MP (°C) IR (cm1) MASS NMR (¾ 13C, 19F)
230 ... (Thin film) 3384, 2987, 1743, 1675, 1622, 1579, 1526, 1506, 1447, 1366, 1344, 1311, 1237, 1201, 1180, 1149, 1117, 1101, 1040, 1003,971, 911,830, 803, 728, 679 HRMS-ESI (m/z) ([M+H]+) calcd for C28H25F6N2O7, 615.1560; found, 615.1570 'HNMR (400 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.20 (d, J= 7.7 Hz, 1H), 6.96 (d, J= 5.4 Hz, 1H), 6.90 (dd, J= 8.2, 6.3 Hz, 2H), 6.84 (dd, 7= 8.0, 6.2 Hz, 2H), 5.72 (d,7= 1.0 Hz, 2H),5.58 (dq, 7= 8.9, 6.2 Hz, 1H), 4.59 (p, 7= 7.3 Hz, 1H), 3.96 (d, 7= 8.8 Hz, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 1.17 (d, 7= 7.3 Hz, 3H) 19F NMR (376 MHz, CDC13) δ -132.49 (d, 7= 20.7 Hz), -132.92 (d, 7= 20.6 Hz), -161.02 (t, 7= 20.6 Hz), -161.33 (t, 7= 20.6 Hz)
232 ... ... ESIMS m/z 320 ([M+H]+) ...
233 ... ... ESIMS m/z 420 ([M+H]+) 'H NMR (400 MHz, CDC13) δ 7.21 (ddd, 7= 11.8, 8.4, 5.2 Hz, 4H), 6.98 (td, 7= 8.6, 5.6 Hz, 4H), 5.67 (dq, 7= 9.2, 6.2 Hz, 1H), 4.80 (d, 7= 7.8 Hz, 1H), 4.06 (dd,7=21.8, 8.4 Hz, 2H), 1.43 (s, 9H), 1.18 (dd, 7= 12.5,6.7 Hz, 6H) 13C NMR (126 MHz, CDC13) δ 172.42, 162.70, 162.62, 160.74, 160.67, 136.89, 136.87, 129.74, 129.67, 129.61, 115.76, 115.59, 115.47, 115.30, 79.79, 72.77, 55.76, 49.40, 30.93, 28.30, 19.00, 18.30
283
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
234 Ά· (Thin film) 3367, 2979, 1708, 1495, 1162, 1049, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3 iF 2NN aC>4, 470.2113; found, 470.2110 1H NMR (400 MHz, CDCh) δ 7.25-7.17 (m, 1H), 7.14 (dd,/=8.4, 5.8 Hz, 1H), 6.91-6.76 (m, 4H), 5.60 (dq, J= 9.8, 6.2 Hz, 1H), 4.94 (d, J= 8.0 Hz, 1H), 4.42 (d,/= 9.8 Hz, 1H), 4.12 (qd, /= 7.2, 2.5 Hz, 1H), 2.37 (s, 3H), 2.32 (s, 3H), 1.42 (s, 9H), 1.29 (d,/= 6.1 Hz, 3H), 0.88 (d,/= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCh) δ-116.52, -117.01.
235 ¥ (Thin film) 3440, 2963, 1708, 1365, 1164, 1051, 908, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C3iH45NNaO4, 518.3241; found, 518.3245 1H NMR (400 MHz, CDCh) δ 7.33-7.17 (m, 8H), 5.77 (dq,/= 10.3, 6.1Hz, 1H), 4.97 (d,/= 7.9 Hz, 1H), 4.10 (dq,/=14.6, 7.2 Hz, 1H), 3.95 (d,/= 10.3 Hz, 1H), 1.41 (s, 9H), 1.26 (s, 9H), 1.25- 1.20 (m, 12H), 0.64 (d,/= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.88, 154.92, 149.54, 149.34, 138.80, 138.25, 127.65, 127.61, 125.59, 125.29, 79.54, 73.50, 57.27, 49.13,34.34,34.29, 31.30, 28.31, 19.36, 17.73.
284
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
236 X o Y (Thin film) 3373, 2960, 1711, 1163, 1050, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C29EUiNNaO4, 490.2928; found, 490.2931 3H NMR (400 MHz, CDC13) δ 7.24-7.17 (m, 4H), 7.167.05 (m, 4H), 5.76 (dq,7 = 10.2, 6.1 Hz, 1H), 4.97 (d,7 = 7.9 Hz, 1H), 4.09 (dq,7= 17.8, 7.3 Hz, 1H), 3.95 (d,7 = 10.3 Hz, 1H), 2.82 (dhept, 7=9.4, 6.9 Hz, 2H), 1.41 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 1.17 (dd, 7= 11.6, 6.9 Hz, 12H), 0.67 (d, 7=7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.87, 154.93, 147.27, 147.10, 139.20, 138.70, 127.91, 127.88, 126.75, 126.44, 79.54, 73.45, 57.42, 49.16,33.64,33.60, 28.31,24.00, 23.97, 23.91, 19.35, 17.79.
237 X (Thin film) 3364, 2976, 1712, 1501, 1450, 1162, 1052, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO4, 462.2615; found, 462.2623 1H NMR (400 MHz, CDCh) δ 7.16-6.89 (m, 6H), 5.73 (dq,7= 10.2, 6.1Hz, 1H), 5.04-4.90 (m, 1H), 4.194.02 (m, 1H), 3.88 (d,7= 10.3 Hz, 1H), 2.17 (dd, 7 = 10.4, 9.0 Hz, 12H), 1.41 (s, 9H), 1.22 (d, 7= 6.1 Hz, 3H), 0.79 (d, 7= 7.1 Hz, 3H).
285
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
238 be O ESIMS m/z 442 ([M+H]+) 3H NMR (400 MHz, CDCfi) 6 7.23 (ddd, 7=16.6, 8.5,5.3 Hz, 4H), 6.97 (td, J= 8.7, 2.2 Hz, 4H), 5.69 (dq,7 = 9.1,6.2 Hz, 1H), 4.93 (d,7 = 7.3 Hz, 1H), 4.08 (dd,7 = 21.8, 8.3 Hz, 2H), 1.43 (s, 9H), 1.18 (dd, J= 13.2, 6.7 Hz, 6H). 13CNMR(101 MHz, CDCfi) δ 172.40, 162.91, 162.84, 160.46, 160.40, 154.90, 136.97, 136.94, 136.66, 129.81, 129.73, 129.69, 129.61, 129.53, 115.76, 115.71, 115.55, 115.50, 115.43, 115.22, 79.65,77.45,77.13,76.81, 72.71, 55.71,49.44, 28.25, 18.92, 18.10.
286
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
239 A ESIMS m/z 420 ([M+H]+) 1H NMR (400 MHz, CDC13) 6 7.23 (ddd, J= 15.9, 8.7,5.4 Hz, 4H), 6.97 (dtd,7=8.7, 6.4, 2.1 Hz, 4H), 5.71 (dq,7 = 9.8, 6.1Hz, 1H), 4.98 (d, J = 7.8 Hz, lH),4.14(dq, J= 14.9, 7.6 Hz, 1H), 4.03 (d, J = 9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d, J= 6.1 Hz, 3H), 0.84 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.75, 162.96, 162.88, 160.51, 160.43, 154.94, 137.01, 136.97, 136.86, 136.82, 129.58, 129.53, 129.51, 129.45, 115.80, 115.59, 115.49, 115.28, 79.71,72.86, 56.20, 49.18, 28.28, 19.17, 18.02.
240 A A (Thin film) 3355,2978, 1711, 1599, 1500, 1162, 954 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3 iF 2NN aC>6, 502.2012; found, 502.2021 1H NMR (400 MHz, CDCI3) δ 7.34 (dd, J= 8.6, 6.7 Hz, 1H), 7.12 (dd, 7= 8.7, 6.7 Hz, 1H), 6.64 - 6.44 (m, 4H), 5.85 (dq, 7= 9.5, 6.1 Hz, 1H), 4.96 (d, 7= 7.8 Hz, 1H), 4.81 (d, 7= 9.8 Hz, 1H), 4.23 - 4.02 (m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.20 (d,7=6.2 Hz, 3H), 0.88 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-113.46, -113.83.
287
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
241 is a ESIMS m/z 398 ([M+H]+) 1H NMR (400 MHz, CDC13) 6 7.30-7.13 (m, 10H), 5.83 (q, 7= 6.4 Hz, 1H), 5.00 (d, 7= 5.4 Hz, 1H), 4.26-4.12 (m, 1H), 1.73 (s, 3H), 1.41 (s, 9H), 1.15 (d, 7= 6.3 Hz, 3H), 0.98 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.77, 154.93, 146.56, 145.15, 128.16, 128.10, 127.92, 127.40, 126.28, 126.14, 79.69, 75.78, 50.38, 49.39, 28.31,23.89, 18.37, 15.98.
242 (Thin film) 3375, 2980, 2934, 2229, 1739, 1708, 1605, 1504 ESIMS m/z 434 ([M+H]+) 1H NMR (400 MHz, CDCI3) δ 7.65 - 7.56 (m, 4H), 7.43 7.33 (m, 4H), 5.85 - 5.73 (m, 1H), 4.87 (d, 7= 7.9 Hz, 1H), 4.19 (dd, 7= 9.3, 2.7 Hz, 1H), 4.17-4.01 (m, 1H), 1.42 (s, 9H), 1.25 (d,7 = 6.2 Hz, 3H), 0.85 (d,7= 7.2 Hz, 3H).
243 X (Thin film) 3357, 2982, 1709, 1617, 1455 ESIMS m/z 520 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.56 (t, 7= 8.1 Hz, 4H), 7.44 - 7.36 (m,4H), 5.89- 5.76 (m, 1H), 4.89 (d,7=7.8 Hz, 1H), 4.19 (d, 7= 9.8 Hz, 1H), 4.12 (t, 7= 7.5 Hz, 1H), 1.41 (s, 9H), 1.26 (d,7=6.2 Hz, 3H), 0.79 (d, 7= 7.2 Hz, 3H).
288
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
244 A A > (Thin film) 3361,2978, 1709, 1494, 1450, 1365, 1162, 1050, 1029, 731, 701 HRMS-ESI (m/z) ([M+H]+) calcd for C23H30NO4, 384.2169; found, 384.2169 1:1 mixture of diastereomers. 3H NMR (500 MHz, CDC13) δ 7.32 - 7.23 (m, 8H), 7.22 7.13 (m, 2H), 5.84-5.72 (m, 1H), 4.93 (d, 7= 7.9 Hz, 1H), 4.77 (d, 7= 6.2 Hz, 1H), 4.15-4.00 (m, 2H), 1.42 (s, 9H), 1.24 (d,7=6.3 Hz, 3H), 1.22 (d, 7= 6.0 Hz, 3H), 1.11 (d, 7= 7.2 Hz, 3H), 0.76 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.83, 172.30, 154.93, 141.50, 141.26, 128.77, 128.73, 128.49, 128.46, 128.23, 128.20, 128.08, 128.05, 126.90, 126.87, 126.66, 79.64, 73.11, 73.03, 57.97, 57.54, 49.46, 49.17, 34.67, 28.32, 25.28, 20.70, 19.30, 19.10, 18.31, 18.00.
245 A (Thin film) 3374, 2977, 1711, 1592, 1489, 1247, 1163, 1029 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H31Cl2NNaO6, 534.1421; found, 534.1427 1H NMR (400 MHz, CDCI3) 6 7.31 (d, 7= 8.2 Hz, 1H), 7.09 (d, 7= 8.1 Hz, 1H), 6.87 (dd, 7= 8.2, 2.0 Hz, 1H), 6.83 (dd,7= 8.1, 2.0 Hz, 1H), 6.79 (dd, 7 = 14.8, 2.0 Hz, 2H), 5.84 (dq, 7 = 12.4, 6.2 Hz, 1H), 4.95 (d,7=7.3 Hz, 1H), 4.81 (d, 7= 9.7 Hz, 1H), 4.26-4.01 (m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.20 (d,7=6.1 Hz, 3H), 0.89 (d, 7= 7.2 Hz, 3H)
289
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
246 >S' > (Thin film) 3360, 2980, 1710, 1598, 1500, 1274, 1160, 1040, 990, 821 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H35F2NNaO6, 530.2325; found, 530.2336 1H NMR (400 MHz, CDCh) δ 7.30 (dd, J= 8.5, 6.8 Hz, 1H), 7.14 (dd, 7= 8.5, 6.8 Hz, 1H), 6.61-6.43 (m, 4H), 5.87 (dq, 7=12.6, 6.3 Hz, 1H), 4.97 (d, 7= 6.9 Hz, 1H), 4.80 (d, 7= 10.1 Hz, 1H), 4.21-4.07 (m, 1H), 4.06 - 3.78 (m,4H), 1.56 1.34 (m, 15H), 1.21 (d,7= 6.1Hz, 3H), 0.90 (d,7=7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.72, -114.20.
247 (Thin film) 3358, 2979, 1711, 1592, 1491, 1247, 1162, 1042 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H35Cl2NNaO6, 562.1734; found, 562.1737 1H NMR (400 MHz, CDCh) 6 7.27 (d, 7= 8.1 Hz, 1H), 7.10 (d, 7= 8.2 Hz, 1H), 6.84 (dd, 7= 5.6, 2.6 Hz, 1H), 6.81 (dd, 7=8.2, 2.0 Hz, 1H), 6.75 (dd, 7=14.9, 2.0 Hz, 2H), 5.86 (dq, 7 = 12.2, 6.1Hz, 1H), 4.98 (d,7=6.9 Hz, 1H), 4.80 (d, 7 = 10.0 Hz, 1H), 4.23 - 4.07 (m, 1H), 4.07-3.75 (m, 4H), 1.52- 1.34 (m, 15H), 1.21 (d, 7= 6.2 Hz, 3H), 0.91 (d, 7= 7.2 Hz, 3H).
290
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
248 (Thin film) 3360, 2977, 1712, 1504, 1259, 1161, 1044 HRMS-ESI (m/z) ([M+Na]+) calcd for C29ELiNNaO6, 522.2826; found, 522.2819 1H NMR (400 MHz, CDCI3) 6 7.25 (d, 7= 7.7 Hz, 1H), 7.12 (d, 7= 7.8 Hz, 1H), 6.69 -6.52(m, 4H), 5.89 (dq,7= 12.3, 6.1 Hz, 1H), 5.03 (d,7 = 6.7 Hz, 1H), 4.88 (d,7= 10.2 Hz, 1H), 4.10 (q, 7 = 12.8, 9.8 Hz, 1H), 4.05 3.78 (m, 4H), 2.26 (s, 3H), 2.24 (s, 3H), 1.53 - 1.33 (m, 15H), 1.22 (d, 7= 6.2 Hz, 3H), 0.86 (d, 7= 7.1 Hz, 3H).
249 NS S' ''N ESIMS m/z 528 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 8.02-7.89 (m, 4H), 7.407.29 (m, 4H), 5.89 - 5.75 (m, 1H), 4.91 (d, 7= 8.0 Hz, 1H), 4.35 (q, 7= 7.1 Hz, 2H), 4.34 (q, 7= 7.1 Hz, 2H), 4.18 (d,7= 9.9 Hz, 1H), 4.16-4.03 (m, 1H), 1.41 (s, 9H), 1.37 (t, ^=7.1 Hz, 6H), 1.24 (d, 7= 6.2 Hz, 3H), 0.81 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.71, 172.69, 166.18, 166.10, 145.69, 145.36, 130.18, 129.91, 129.56, 129.31, 128.25, 128.12, 72.36, 60.98, 60.95, 57.67, 28.29, 19.18, 18.09, 14.29, 14.28.
291
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
250 CS5 (Thin film) 3378, 2979, 1707, 1592, 1453, 1134, 1050, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3 iF 2NN aO6, 502.2012; found, 502.2022 1H NMR (400 MHz, CDC13) 6 6.65-6.51 (m, 4H), 6.46 (tt, J= 10.3,2.3 Hz, 2H), 5.67 (dq, J= 10.0,6.1 Hz, 1H), 4.98 (d, 7= 7.9 Hz, 1H), 4.14 (dd, 7 = 10.5, 4.8 Hz, 1H), 3.92 (d, 7= 9.9 Hz, 1H), 3.76 (s, 3H), 3.75 (s, 3H), 1.42 (s, 9H), 1.24 (d,7 = 6.2 Hz, 3H), 0.88 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-110.64, -111.21.
251 «Α is A (Thin film) 3375, 2978, 1708, 1593, 1456, 1149, 1059, 729 HRMS-ESI (m/z) ([M+Na]+) calcd for C2-H3-NNaOx, 526.2411; found, 526.2409 1H NMR (400 MHz, CDCh) 6 6.45 (dd, 7=4.5, 2.2 Hz, 4H), 6.28 (dt, 7=13.7, 2.2 Hz, 2H), 5.73 (dq, 7 = 10.3, 6.1Hz, 1H), 5.00 (d, 7=7.9 Hz, 1H), 4.12 (tt, 7= 7.1, 3.3 Hz, 1H), 3.87 (d, 7= 10.4 Hz, 1H), 3.75 (s, 6H), 3.73 (s, 6H), 1.42 (s, 9H), 1.24 (d, 7= 6.1 Hz, 3H), 0.84 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.84, 160.97, 160.78, 154.94, 143.51, 143.22, 106.45, 106.20, 98.58, 98.44, 79.63, 72.69, 58.27, 55.28, 55.26, 49.25, 28.31, 19.27, 18.07.
292
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
252 CN A A A (Thin film) 3370, 2978, 1708, 1594, 1454, 1292, 1153, 1051, 729 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO6, 494.2513; found, 494.2510 1H NMR (400 MHz, CDCI3) δ 6.69 (s, 2H), 6.66 - 6.62 (m, 2H), 6.54 (s, 1H), 6.50 (s, 1H), 5.72 (dq, 7 = 10.4, 6.1Hz, 1H), 5.00 (d, 7=7.9 Hz, 1H), 4.22 - 4.00 (m, 1H), 3.86 (d, J= 10.4 Hz, 1H), 3.74 (s, 3H), 3.73 (s, 3H), 2.28 (s, 3H), 2.25 (s, 3H), 1.41 (s, 9H), 1.22 (d,7 = 6.2 Hz, 3H), 0.80 (d,7= 7.1Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.85, 159.78, 159.65, 154.93, 142.79, 142.49, 139.72, 139.28, 121.29, 112.72, 112.69, 111.34, 110.84, 79.59, 72.99, 57.93, 55.12, 55.11,49.24, 28.32,21.65,21.58, 19.31, 18.02.
293
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
253 (Thin film) 3377, 2978, 1711, 1508, 1252, 1163, 1041,732 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO6, 494.2513; found, 494.2493 1H NMR (400 MHz, CDCf) 6 7.00 (ddd, J= 13.3, 7.6,0.9 Hz, 2H), 6.85-6.68 (m, 4H), 5.78 (dq, J= 10.3,6.1 Hz, 1H), 5.11 -4.82 (m, 1H), 4.12 (qd, 7= 7.1, 2.3 Hz, 1H), 3.94 (d, J= 10.2 Hz, 1H), 3.79 (s, 3H), 3.78 (s, 3H),2.14(s, 3H),2.12(s, 3H), 1.41 (s, 9H), 1.24 (d,7 = 6.1 Hz, 3H), 0.80 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDC13) δ 172.87, 157.86, 157.65, 154.93, 140.45, 140.25, 130.75, 130.47, 125.22, 124.79, 119.74, 119.69, 109.82, 109.77, 79.64, 73.09, 57.95, 55.27, 55.25,49.29, 28.32, 19.35, 18.06, 15.80, 15.75.
254 > (Thin film) 3377, 2979, 1706, 1513, 1274, 1161, 1025, 729 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3 iF 2NN aO6, 502.2012; found, 502.2008 1H NMR (400 MHz, CDCf) δ 7.06 - 6.92 (m, 4H), 6.88 (td, 7= 8.7, 4.6 Hz, 2H), 5.63 (dq, 7=9.6, 6.2 Hz, 1H), 4.99 (d, 7= 7.9 Hz, 1H), 4.13 (p, 7= 6.9 Hz, 1H), 3.91 (d, 7= 9.6 Hz, 1H), 3.84 (s, 3H), 3.83 (s, 3H), 1.42 (s, 9H), 1.22 (d,7 = 6.2 Hz, 3H), 0.90 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCf) δ-134.14, -134.59.
294
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
255 & QS (Thin film) 3376, 2978, 1711, 1502, 1247, 1163, 1052, 730 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO6, 494.2513; found, 494.2515 1H NMR (400 MHz, CDC13) 6 7.05 (ddd, J= 7.8, 4.8, 2.3 Hz, 2H), 7.01 (d, 7= 2.2 Hz, 2H), 6.70 (t, 7= 8.8 Hz, 2H), 5.68 (dq, 7= 10.1,6.1 Hz, 1H), 4.98 (d, 7= 7.9 Hz, 1H), 4.12 (ddp, 7= 11.8, 7.9, 4.3 Hz, 1H), 3.85 (d, 7= 10.2 Hz, 1H), 3.76 (s, 3H), 3.74 (s, 3H),2.16(s, 3H),2.14(s, 3H), 1.41 (s, 9H), 1.21 (d,7 = 6.1 Hz, 3H), 0.82 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDC13) δ 172.87, 156.53, 156.36, 154.94, 133.77, 133.55, 130.40, 130.30, 126.81, 126.38, 126.06, 125.86, 110.05, 109.91, 79.58, 73.47,56.31,55.32, 55.27, 49.28, 28.32, 19.34, 18.15, 16.32, 16.24.
256 Q\ OS SR (Thin film) 3355,2978, 1712, 1497, 1223, 1161, 1047, 730 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO8, 526.2411; found, 526.2405 1H NMR (400 MHz, CDC13) 6 7.04 (d, 7= 3.0 Hz, 1H), 6.86 (d, 7= 3.0 Hz, 1H), 6.74 (dd, 7 = 19.1, 8.9 Hz, 2H), 6.66 (ddd, 7= 9.1, 6.3, 3.0 Hz, 2H), 5.88 (dq, 7=10.0, 6.2 Hz, 1H), 5.03 (d,7=7.8 Hz, 1H), 4.91 (d, 7= 10.1 Hz, 1H), 4.12 (m, 1H), 3.80 (s, 3H), 3.73 (s, 3H), 3.71 (s, 3H), 3.70 (s, 3H), 1.41 (s, 9H), 1.30- 1.19 (m, 3H), 0.86 (d, 7= 7.2 Hz, 3H).
295
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
257 (Thin film) 3364, 2978, 1710, 1497, 1245, 1160, 1045, 730 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NNaO6, 494.2513; found, 494.2507 XH NMR (400 MHz, CDC13) 6 7.05 (d, 7= 8.4 Hz, 1H), 6.99 (d, 7= 8.3 Hz, 1H), 6.88 (d, 7= 2.7 Hz, 1H), 6.81 (d, 7= 2.7 Hz, 1H), 6.63 (ddd, 7 = 15.9, 8.3, 2.7 Hz, 2H), 5.63 (dq,7= 10.0, 6.1Hz, 1H), 4.99 (d, 7= 7.9 Hz, 1H), 4.43 (d, 7= 10.1 Hz, 1H), 3.72 (s, 3H), 3.72 (s, 3H), 2.32 (s, 3H), 2.26 (s, 3H), 1.461.39 (m, 10H), 1.30 (d, 7= 6.2 Hz, 3H), 0.86 (d,7=7.2 Hz, 3H).
258 sc X HRMS-ESI (m/z) ([M+H]+) calcd for C27H37NO8Na, 526.2411; found, 526.2405 XH NMR (400 MHz, CDC13) 6 7.08-6.91 (m, 3H), 6.896.82 (m, 1H), 6.76 (ddd, 7 = 8.0, 3.8, 1.7 Hz, 2H), 5.765.53 (m, 1H), 5.15-5.07 (m, 1H), 5.07-4.93 (m, 1H), 4.21-4.03 (m, 1H), 3.903.80 (m, 9H), 3.76 -3.72 (m, 3H), 1.47- 1.37 (m, 9H), 1.24 (t, 7= 6.0 Hz, 3H), 1.14 (d, 7= 6.9 Hz, 1H), 0.86 (d, 7= 7.0 Hz, 2H). 13CNMR(101 MHz, CDC13) δ 172.73, 172.19, 152.83, 152.74, 147.49, 147.21, 135.15, 135.02, 134.77, 134.64, 123.63, 123.58, 123.52, 120.98, 120.94, 120.51, 120.38, 110.86, 110.74, 110.67, 73.58, 60.35, 60.29, 60.20, 55.65,42.03,41.98, 28.31, 18.90, 18.77, 18.52, 18.19.
296
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
259 (Thin film) 3362, 2981, 1713, 1618, 1501, 1475, 1430, 1293, 1252, 1165, 1102, 1058, 951, 748 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H29F4NOeNa, 538.1823; found, 538.1826 1H NMR (400 MHz, CDCh) δ 7.09 - 7.02 (m, 1H), 6.886.74 (m, 3H), 5.70 - 5.59 (m, 1H), 4.95 (d, 7= 7.9 Hz, 1H), 4.85 (d, 7= 9.7 Hz, 1H), 4.22 - 4.07 (m, 1H), 3.97 (d, 7= 2.4 Hz, 3H), 3.86 (d, 7= 2.1 Hz, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.96 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.67, 154.91, 151.50, 151.26 (d, 7= 11.3 Hz), 149.47 (d, 7= 11.3 Hz), 149.28 (d, 7= 11.5 Hz), 147.24, 147.18, 147.03, 146.97, 145.35, 145.24, 143.36, 143.25, 129.90 (d, 7 = 3.5 Hz), 129.59, 123.09122.78 (m), 122.38, 110.96 - 110.60 (m), 79.81, 72.19, 61.23, 61.17, 49.21, 42.46, 28.29, 18.87, 18.29.
297
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
260 Se (Thin film) 3382, 2977, 2930, 1715, 1501, 1453, 1365, 1249, 1167, 1049, 811, 734 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NO4Na, 462.2615; found, 462.2615 1H NMR (400 MHz, CDCh) δ 7.07-6.84 (m, 6H), 5.64 (dq, 7= 11.9, 5.9 Hz, 1H), 4.96 (d, J= 8.1 Hz, 1H), 4.44 (d, 7= 10.3 Hz, 1H), 4.18 4.02 (m, 1H), 2.35 (s, 3H), 2.29 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.42 (s, 9H), 1.27 (d, J= 6.1 Hz, 3H), 0.82 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.97, 154.93, 139.18, 138.55, 135.43, 135.04, 133.58, 133.35, 130.57, 130.28, 128.58, 127.87, 127.22, 126.90, 79.67, 74.72, 49.26, 47.36, 34.67, 28.32, 21.26, 21.22, 19.77, 19.73, 18.86.
298
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
261 A A (Thin film) 3364, 2977, 1713, 1499, 1452, 1365, 1209, 1164, 1049, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H37NO4Na, 462.2615; found, 462.2614 XH NMR (400 MHz, CDC13) δ 7.15 (d, J= 8.5 Hz, 1H), 7.11 (d, 7= 8.5 Hz, 1H), 6.96 -6.88(m, 4H), 5.64 (dq,7 = 9.9, 6.1Hz, 1H), 4.94 (d,7 = 7.9 Hz, 1H), 4.42 (d,7= 10.0 Hz, 1H), 4.17-4.05 (m, 1H), 2.34 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H), 2.22 (s, 3H), 1.42 (s, 9H), 1.28 (d,7 = 6.2 Hz, 3H), 0.84 (d,7= 7.1Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.88, 154.95, 136.54, 136.39, 136.19, 136.07, 135.85, 135.52, 131.49, 131.16, 127.74, 127.12, 126.82, 126.56, 79.63, 74.68, 49.24, 46.84, 34.67, 31.59, 28.32, 20.84, 20.10, 20.06, 18.94.
299
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
262 & (Thin film) 3381,2979, 1711, 1609, 1589, 1495, 1454, 1366, 1241, 1165, 1049, 810, 729 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H31F2NO4Na, 470.2113; found, 470.2120 3H NMR (400 MHz, CDC13) 6 7.11 (dd, 7=8.4, 6.0 Hz, 1H), 7.07 (dd, J= 8.5, 6.0 Hz, 1H), 7.00 (dd, 7=10.6, 2.6 Hz, 1H), 6.90 (dd,7 = 10.3, 2.7 Hz, 1H), 6.876.77 (m, 2H), 5.55 (dq,7 = 9.6, 6.2 Hz, 1H), 4.95 (d,7 = 7.2 Hz, 1H), 4.45 (dt,7= 9.6, 1.2 Hz, 1H), 4.20-4.08 (m, 1H), 2.34 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.31 (d, J= 6.2 Hz, 3H), 0.89 (d,7= 7.3 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.77, 161.36 (d, J= 243.9 Hz), 161.32 (d,7= 243.5 Hz), 154.96, 140.69 (d, 7= 6.7 Hz), 140.10 (d, 7 = 6.4 Hz), 132.38 (d, 7= 3.2 Hz), 132.07, 132.01, 131.69 (d, 7= 7.9 Hz), 114.83 (d,7 = 22.3 Hz), 114.34 (d,7 = 22.2 Hz), 113.67 (d, 7= 20.7 Hz), 113.35 (d, 7= 20.7 Hz), 79.79, 73.85, 49.16, 47.74, 34.67, 31.59, 28.31, 19.39, 19.35, 18.82, 18.05.
300
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
263 (Thin film) 2978, 1710, 1497, 1454, 1366, 1249, 1209, 1160, 1036, 814, 728 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H31F2NO6, 502.2012; found, 502.2011 1H NMR (400 MHz, CDCR) δ 7.01 - 6.86 (m, 3H), 6.82 (dd, J= 5.8, 3.1Hz, 1H), 6.74-6.64 (m, 2H), 5.82 (dq, 7= 12.0, 6.2 Hz, 1H), 4.97 (d, 7= 7.8 Hz, 1H), 4.67 (d, 7= 10.5 Hz, 1H), 4.214.09 (m, 1H), 3.74 (s, 6H), 1.42 (s, 9H), 1.29 (d,7=6.2 Hz, 3H), 0.89 (d, 7= 7.3 Hz, 3H). 13CNMR(126 MHz, CDCb) δ 172.70, 156.13, 155.90, 155.74, 155.57, 154.90, 154.24, 154.00, 127.94 (d, 7= 15.8 Hz), 127.63 (d,7= 16.2 Hz), 116.24 (d, 7= 24.9 Hz), 115.97 (d, 7= 24.8 Hz), 115.14, 114.12, 113.16 (d, 7 = 8.3 Hz), 113.03 (d,7=8.2 Hz), 79.69, 71.79, 55.70, 49.15, 43.38, 34.66, 28.30, 19.00, 18.12.
301
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
264 \£- (Thin film) 2978, 2936, 1712, 1623, 1585, 1506, 1445, 1366, 1288, 1159, 1031, 950, 834, 731 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H31F2NO6Na, 502.2012; found, 502.2016 3H NMR (400 MHz, CDCfi) δ 7.27 (t, J= 8.6 Hz, 1H), 7.16 (t, J= 8.5 Hz, 1H), 6.65 -6.50 (m, 4H), 5.82-5.72 (m, 1H), 4.96 (d, 7= 7.9 Hz, 1H), 4.60 (d, 7= 10.2 Hz, 1H), 4.21-4.09 (m, 1H), 3.75 (s, 3H), 3.74 (s, 3H), I. 42 (s, 9H), 1.26 (d,7=6.1 Hz, 3H), 0.92 (d, 7= 7.3 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 172.73, 161.24 (d, 7= 245.7 Hz), 161.01 (d,7= 246.0 Hz), 159.73 (d,7= II. 1 Hz), 159.50 (d, 7= 11.3 Hz), 154.93, 129.86 (d, 7 = 5.8 Hz), 129.31, 119.70 (d, 7 = 14.6 Hz), 119.41 (d,7 = 15.1 Hz), 110.15 (d, 7=2.9 Hz), 109.77 (d, 7= 3.0 Hz), 101.81 (d, 7= 26.8 Hz), 79.67, 72.07, 55.51, 49.19, 41.73, 28.31, 19.01, 18.24.
302
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
265 Ύ NS SS ss (Thin film) 2982, 1714, 1507, 1456, 1417, 1327, 1243, 1212, 1166, 1123, 1033, 860, 739 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H31F6NO6Na, 602.1948; found, 602.1948 1H NMR (400 MHz, CDC13) 6 7.53 (d, 7= 8.0 Hz, 1H), 7.31 (d, 7= 8.0 Hz, 1H), 7.16 (d, 7= 7.6 Hz, 1H), 7.147.10 (m, 1H), 7.01 (dd,7 = 15.7, 1.7 Hz, 2H), 6.015.91 (m, 1H), 4.97 (d,7=9.7 Hz, 1H), 4.93 (d, 7= 8.0 Hz, 1H), 4.18-4.06 (m, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 1.41 (s, 9H), 1.23 (d,7=6.2 Hz, 3H), 0.83 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) 6 172.77, 157.43, 154.92, 132.51, 132.36, 130.03, 129.43, 125.01, 122.84, 117.27 (q, 7= 3.9 Hz), 116.99 (q, 7= 3.3 Hz), 107.64 (q, 7= 3.0 Hz), 107.44 (q, 7=4.1 Hz), 79.75, 71.76, 55.70, 49.17, 28.29, 18.94, 18.11.
303
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
266 (Thin film) 3355,2961, 1712, 1493, 1366, 1266, 1160, 1095 HRMS-ESI (m/z) ([M+Na]+) calcd for C27H35F2NO6Na, 530.2325; found, 530.2331 1H NMR (400 MHz, CDC13) δ 7.39 (dd, J= 8.7, 5.6 Hz, 1H), 7.27 - 7.22 (m, 1H), 7.16-7.05 (m,2H), 6.986.89 (m, 2H), 5.58 (dq, 7 = 8.8, 6.2 Hz, 1H), 4.95 (d,7 = 7.4 Hz, 1H), 4.68 (d,7=9.1 Hz, 1H), 4.61 (d, 7 = 12.4 Hz, 1H), 4.53 (d, 7 = 12.5 Hz, 1H), 4.42 (d, 7 = 12.3 Hz, 2H), 4.18-4.06 (m, 1H), 3.42 (s, 3H), 3.41 (s, 3H), 1.42 (s, 9H), 1.27 (d,7 = 6.2 Hz, 3H), 0.90 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDC13) δ -115.52, -115.88.
267 s (Thin film) 3356, 2977, 1712, 1494, 1366, 1160, 1116,1096 HRMS-ESI (m/z) ([M+Na]+) calcd for C29H39F2NOr,Na, 558.2638; found, 558.2638 1H NMR (400 MHz, CDC13) 6 7.40 (dd, 7=8.7, 5.6 Hz, 1H), 7.24 (dd, 7= 8.7, 5.6 Hz, 1H), 7.13 (t, 7= 3.2 Hz, 1H), 7.10 (t, 7= 3.2 Hz, 1H), 6.96-6.88 (m, 2H), 5.59 (dq, 7= 8.7, 6.2 Hz, 1H), 4.98 (d, 7= 7.5 Hz, 1H), 4.69 (d, 7= 8.9 Hz, 1H), 4.65 (d, 7= 12.5 Hz, 1H), 4.59 (d,7= 12.6 Hz, 1H), 4.46 (d,7 = 12.5 Hz, 1H), 4.45 (d,7 = 12.6 Hz, 1H), 4.20-4.06 (m, 1H), 3.62 -3.44 (m, 4H), 1.42 (s, 9H), 1.321.18 (m,9H), 0.91 (d,7=7.2 Hz, 3H). 19F NMR (376 MHz, CDC13) δ-115.64, -115.97.
304
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (Y, 13c, 19f)
268 A «s Y (Thin film) 3372, 2978, 2936, 2835, 1713, 1582, 1500, 1457, 1366, 1306, 1257, 1211, 1166, 1098, 1048, 910, 752, 734 HRMS-ESI (m/z) ([M+H]+) calcd for C27H37NO6Na, 494.2513; found, 494.2490 3H NMR (400 MHz, CDC13) 6 7.07 (q, 7= 8.0 Hz, 4H), 6.93 (dd, 7= 7.7, 3.2 Hz, 2H), 6.85 (t, 7= 7.5 Hz, 2H), 6.74-6.62 (m, 4H), 5.65 (dqd, 7=9.3, 6.1, 3.1Hz, 2H), 4.96 (d, 7= 7.4 Hz, 1H), 4.81 (s, 1H), 4.60 (dd, 7 = 9.9, 6.0 Hz, 2H), 4.09 (dt, 7= 15.3, 6.9 Hz, 2H), 3.79 (s, 6H), 3.77 (s, 3H), 3.76 (s, 3H), 2.27 (d, 7= 7.5 Hz, 6H), 2.20 (s, 6H), 1.43 (s, 9H), 1.42- 1.38 (m, 12H), 1.26 (t, 7= 6.0 Hz, 6H), 0.83 (d, 7= 7.2 Hz, 3H).
269 A Y Y (Thin film) 3357, 2978, 1712, 1500, 1467, 1452, 1420, 1365, 1250, 1207, 1162, 1091, 1053, 1006, 909, 866, 765, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C27H37NO6Na, 494.2513; found, 494.2509 3H NMR (400 MHz, CDC13) δ 7.30 (dd, 7= 7.6, 1.4 Hz, 2H), 7.14 (d, 7= 7.7 Hz, 2H), 7.11-6.99 (m, 4H), 6.99 - 6.87 (m, 4H), 5.735.49 (m,2H), 5.20 (d,7=7.3 Hz, 1H), 5.14-4.98 (m, 3H), 4.11 (s,2H), 3.81 (s, 3H), 3.76 (s, 3H), 3.74 (s, 3H),3.71 (s, 3H), 2.352.23 (m, 12H), 1.43 (d,7= 12.5 Hz, 18H), 1.26 (dd,7= 6.2,2.1 Hz, 6H), 1.09 (d,7 = 6.8 Hz, 3H), 0.82 (d,7=7.1 Hz, 3H).
305
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
270 AG (Thin film) 3364, 2976, 2935, 2836, 1711, 1608, 1585, 1504, 1453 ESIMS m/z 521 ([M+NH4]+) 1H NMR (400 MHz, CDCh) 6 7.31 (d,/= 8.5 Hz, 1H), 7.11 (d,/= 8.4 Hz, 1H), 6.41 (dt,/=5.2,2.6Hz,2H), 6.37 (dt,/= 5.6, 2.7 Hz, 2H), 5.84 (dq,/= 9.8, 6.2 Hz, 1H), 5.01 (d,/= 7.9 Hz, 1H), 4.79 (d,/= 9.9 Hz, 1H), 4.18-4.06 (m, 1H), 3.81 (s, 3H), 3.74 (s, 6H), 3.73 (s, 3H), 1.42 (s, 9H), 1.20 (d,/= 6.2 Hz, 3H), 0.88 (d,/= 7.2 Hz, 3H).
271 NS o ¥ (Thin film) 3365, 2977, 2934, 1712, 1611, 1504, 1452 ESIMS m/z 489 ([M+NH4]+) 3H NMR (300 MHz, CDCh) 6 7.28 (d,/= 7.8 Hz, 1H), 7.13-7.03 (m, 1H), 6.696.56 (m, 4H), 5.86 (dq,/= 9.8, 6.2 Hz, 1H), 5.01 (d,/= 7.8 Hz, 1H), 4.88 (d,/= 9.9 Hz, 1H), 4.20-3.98 (m, 1H), 3.81 (s, 3H), 3.73 (s, 3H), 2.27 (s, 3H), 2.26 (s, 3H), 1.41 (s, 9H), 1.21 (d,/ = 6.1 Hz, 3H), 0.85 (d,/= 7.1Hz, 3H).
306
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
272 (Thin film) 3366, 2978, 2933,2835, 1714, 1501, 1453 ESIMS m/z 489 ([M+NH4]+) 'Η NMR (300 MHz, CDCh) δ 7.18 (d, J= 2.1 Hz, 1H), 7.03 (d, 7= 2.2 Hz, 1H), 6.95 -6.88 (m, 2H), 6.73 (d,7= 8.3 Hz, 1H), 6.68 (d,7=8.3 Hz, 1H), 5.83 (dq, 7 = 12.2, 6.1 Hz, 1H), 5.03 (d,7=7.9 Hz, 1H), 4.93 (d, 7 = 10.3 Hz, 1H), 4.19-4.05 (m, 1H), 3.81 (s, 3H), 3.72 (s, 3H), 2.24 (s, 3H), 2.21 (s, 3H), 1.42 (d, 7= 0.6 Hz, 9H), 1.21 (d, 7= 6.1 Hz, 3H), 0.84 (d, 7= 7.2 Hz, 3H).
273 A ESIMS m/z 480 ([M+H]+) 1H NMR (400 MHz, CDCh) δ 7.05 - 6.93 (m, 2H), 6.916.75 (m, 4H), 5.71 (dq,7 = 10.1, 6.2 Hz, 1H), 4.91 (d,7 = 7.9 Hz, 1H), 4.20 - 4.07 (m, 1H), 3.96 (d,7= 10.0 Hz, 1H), 3.86 (s, 3H), 3.85 (s, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.1 Hz, 3H), 0.86 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-137.12, -137.69.
274 □ ESIMS m/z 472 ([M+H]+) 1H NMR (400 MHz, CDCh) δ 7.22 - 7.04 (m, 2H), 6.77 6.56 (m, 4H), 5.60 (dq,7 = 9.8, 6.1 Hz, 1H), 4.95 (d,7 = 7.9 Hz, 1H), 4.36 (d, 7= 10.0 Hz, 1H), 4.20 - 4.03 (m, 1H), 3.75 (s, 3H), 3.73 (s, 3H), 2.35 (s, 3H), 2.31 (s, 3H), 1.42 (s, 9H), 1.27 (d,7=6.2 Hz, 3H), 0.87 (d, 7= 7.2 Hz, 3H).
307
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
275 A ίΎ ESIMS m/z 432 ([M+H]+)
276 ESIMS m/z 432 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.35 - 7.28 (m, 2H), 7.25 7.20 (m, 2H), 7.20 - 7.09 (m, 2H), 6.65 - 6.51 (m, 2H), 5.81 (dq, 7= 10.0,6.2 Hz, 1H), 4.92 (d, 7= 8.0 Hz, 1H), 4.53 (d, 7= 10.1 Hz, 1H), 4.19-4.04 (m, 1H), 3.83 (s, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.78 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-113.26.
277 Γ3 ESIMS m/z 416 ([M+H]+) 1H NMR (400 MHz, CDCI3) δ 7.33 - 7.20 (m, 5H), 7.197.10 (m, 1H), 6.92-6.81 (m, 2H), 5.75 (dq, 7= 10.3,6.1 Hz, 1H), 4.91 (d, 7= 8.0 Hz, 1H), 4.26 (d,7= 10.3 Hz, 1H), 4.18-4.02 (m, 1H), 2.38 (s, 3H), 1.42 (s, 9H), 1.25 (d,7=6.1 Hz, 3H), 0.79 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-116.70.
308
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
278 A A > ESIMS m/z 432 ([M+H]+) 1H NMR (400 MHz, CDCh) δ 7.32-7.12 (m, 6H), 6.59 (td, J= 8.3, 2.6 Hz, 1H), 6.52 (dd, 7= 10.9, 2.5 Hz, 1H), 5.79 (dq, J= 10.1,6.1 Hz, 1H), 5.00 (d, 7= 8.2 Hz, 1H), 4.51 (d, 7= 10.2 Hz, 1H), 4.19-4.04 (m, 1H), 3.75 (s, 3H), 1.41 (s, 9H), 1.21 (d, 7= 6.1 Hz, 3H), 0.86 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.59.
279 A ESIMS m/z 416 ([M+H]+) 1H NMR (400 MHz, CDCh) δ 7.38-7.15 (m, 6H), 6.906.77 (m, 2H), 5.72 (dq,7= 10.1, 6.1 Hz, 1H), 4.97 (d,7 = 8.4 Hz, 1H), 4.23 (d,7= 10.1 Hz, 1H), 4.19-4.03 (m, 1H), 2.31 (s, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.1 Hz, 3H), 0.82 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ -117.14.
309
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
280 SN > ESIMS m/z 446 ([M+H]+) 3H NMR (400 MHz, CDCf) δ 7.19 (d, J= 8.0 Hz, 2H), 7.13 (dt, J= 8.1, 6.5 Hz, 1H), 7.04 (d, 7= 7.9 Hz, 2H), 6.61 - 6.50 (m, 2H), 5.78 (dq, 7=9.7, 6.1Hz, 1H), 4.94 (d, 7= 7.8 Hz, 1H), 4.49 (d, 7= 9.8 Hz, 1H), 3.82 (s, 3H), 2.26 (s, 3H), 1.42 (s, 9H), 1.21 (d,7 = 6.2 Hz, 3H), 0.82 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCf) δ-113.47.
281 S' A A ESIMS m/z 430 ([M+H]+) 1H NMR (400 MHz, CDCf) 6 7.31 -7.25 (m, 1H), 7.167.09 (m,2H), 7.04 (d,7=7.8 Hz, 2H), 6.91 - 6.80 (m, 2H), 5.72 (dq, 7= 10.2,6.2 Hz, 1H), 4.92 (d, 7= 8.0 Hz, 1H), 4.22 (d, 7= 10.2 Hz, 1H), 4.18-4.02 (m, 1H), 2.37 (s, 3H), 2.25 (s, 3H), 1.42 (s, 9H), 1.24 (d,7=6.1 Hz, 3H), 0.83 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCf) δ -116.91.
310
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
282 A A A? ESIMS m/z 446 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 7.26 (dd, 7=8.5, 6.5 Hz, 1H), 7.16 (d, 7= 8.1 Hz, 2H), 7.06 (d, 7= 8.0 Hz, 2H), 6.58 (td, 7= 8.3, 2.6 Hz, 1H), 6.52 (dd, 7=10.9, 2.5 Hz, 1H), 5.77 (dq,7 = 10.1, 6.1 Hz, 1H), 5.01 (d,7 = 8.4 Hz, 1H), 4.48 (d,7= 10.3 Hz, 1H), 4.19-4.04 (m, 1H), 3.76 (s, 3H), 2.27 (s, 3H), 1.41 (s, 9H), 1.21 (d,7 = 6.1 Hz, 3H), 0.85 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) 6-113.81.
283 a ESIMS m/z 430 ([M+H]+) 3H NMR (400 MHz, CDCh) 6 7.31 (dd, 7=8.6, 5.8 Hz, 1H), 7.14-7.04 (m, 4H), 6.87 - 6.77 (m, 2H), 5.70 (dq,7= 10.1, 6.1Hz, 1H), 4.97 (d, 7= 7.8 Hz, 1H), 4.19 (d, 7= 10.3 Hz, 1H), 4.174.02 (m, 1H), 2.31 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 0.81 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) 6-117.35.
311
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
284 A A ESIMS m/z 450 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 7.35 -7.22 (m, 2H), 7.12 (dd, J= 8.4, 6.5 Hz, 1H), 6.98 - 6.84 (m, 2H), 6.71 6.48 (m, 2H), 5.78 (dq,7 = 12.1, 6.3 Hz, 1H), 4.91 (d,7 = 8.0 Hz, 1H), 4.49 (d,7= 9.9 Hz, 1H), 4.25 - 4.02 (m, 1H), 3.82 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 0.84 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) 6-112.92, -116.53.
285 X ESIMS m/z 434 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 7.31 -7.16 (m, 3H), 7.006.79 (m, 4H), 5.70 (dq,7 = 10.3, 6.1Hz, 1H), 4.89 (s, 1H), 4.25 (d, 7= 10.2 Hz, 1H), 4.18-4.04 (m, 1H), 2.36 (s, 3H), 1.42 (s, 9H), 1.25 (d, 7=6.1 Hz, 3H), 0.87 (d, 7= 7.0 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-116.06, -116.38.
312
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
286 X X ESIMS m/z 450 ([M+H]+) 1H NMR (400 MHz, CDC13) 6 7.25 -7.19 (m, 3H), 6.996.90 (m,2H), 6.60 (td, J = 8.3, 2.5 Hz, 1H), 6.54 (dd,7 = 10.9, 2.5 Hz, 1H), 5.74 (dq, 7= 11.9, 6.1 Hz, 1H), 4.94 (d, J= 7.8 Hz, 1H), 4.48 (d, 7= 10.2 Hz, 1H), 4.194.05 (m, 1H), 3.77 (s, 3H), 1.42 (s, 9H), 1.20 (d,7=6.2 Hz, 3H), 0.86 (d, 7= 7.3 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ -113.32, -116.11.
287 V· A V· X X ESIMS m/z 434 ([M+H]+) 1H NMR (400 MHz, CDC13) δ 7.30 (dd, 7= 8.6, 5.7 Hz, 1H), 7.24-7.11 (m, 2H), 7.01 - 6.93 (m, 2H), 6.92 6.69 (m, 2H), 5.67 (dq,7 = 10.0, 6.2 Hz, 1H), 4.92 (d,7 = 6.4 Hz, 1H), 4.22 (d,7= 10.0 Hz, 1H), 4.18-4.01 (m, 1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 0.83 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ -115.53, -116.86.
313
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
288 A A A (Thin film) 3364, 2978, 1709, 1600, 1496, 1161 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3iF2NNaO5, 486.2063; found, 486.2063 XH NMR (400 MHz, CDC13) 6 7.21 (dd, 7=8.5, 6.6 Hz, 1H), 7.16 (dd,7= 8.5, 5.9 Hz, 1H), 6.82 (tt,7= 8.4, 4.1 Hz, 2H), 6.59 (td, 7= 8.2, 2.5 Hz, 1H), 6.53 (dd,7 = 10.8,2.4 Hz, 1H), 5.67 (dq,7 = 12.3, 6.1Hz, 1H), 4.97 (d, 7= 6.5 Hz, 1H), 4.73 (d,7= 10.2 Hz, 1H), 4.25-4.04 (m, 1H), 3.78 (s, 3H), 2.42 (s, 3H), 1.42 (s, 9H), 1.21 (d, 7= 6.1 Hz, 3H), 0.92 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-113.52, -116.98.
289 &ΐ A A (Thin film) 3364, 2979, 1710, 1601, 1501, 1162 HRMS-ESI (m/z) ([M+Na]+) calcd for CXYxFjNNaOs, 490.1812; found, 490.1809 1H NMR (400 MHz, CDCI3) δ 7.32 - 7.27 (m, 1H), 7.23 7.14 (m, 1H), 6.81-6.71 (m, 2H), 6.61 (td, 7= 8.3, 2.5 Hz, 1H), 6.54 (dd,7=10.8, 2.5 Hz, 1H), 5.79 (dq,7= 11.8, 6.1 Hz, 1H), 4.95 (d,7 = 7.1 Hz, 1H), 4.76 (d,7= 10.1 Hz, 1H), 4.21 -4.05 (m, 1H), 3.76 (s, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.3 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-112.15 (d, 7= 44.2 Hz), 112.17 (d, 7= 44.3 Hz),112.91.
314
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
290 γ (Thin film) 3365, 2979, 1709, 1497, 1450, 1160 HRMS-ESI (m/z) ([M+Na]+) calcd for C25H3iF2NNaO5, 486.2063; found, 486.2067 1H NMR (400 MHz, CDC13) δ 7.30 (dd, J= 8.4, 6.2 Hz, 1H), 7.03 (dd, J= 8.6, 6.6 Hz, 1H), 6.80 (d, 7= 8.7 Hz, 2H), 6.58 (d, 7= 9.2 Hz, 2H), 5.65 (dq, 7= 9.9, 6.1 Hz, 1H), 4.93 (d, 7= 6.9 Hz, 1H), 4.73 (d, 7= 9.9 Hz, 1H), 4.18-4.04 (m, 1H), 3.84 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.24 (d,7=6.2 Hz, 3H), 0.85 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-112.94, -117.45.
291 (Thin film) 3364, 2980, 1711, 1499, 1163 HRMS-ESI (m/z) ([M+Na]+) calcd for C24H28F 3NN aCfi, 474.1862; found, 474.1863 1H NMR (400 MHz, CDCI3) δ 7.30 (dd, 7= 8.1, 5.8 Hz, 1H), 7.18-7.07 (m, 1H), 6.90-6.75 (m, 4H), 5.67 (dq,7=11.7, 6.5 Hz, 1H), 4.92 (d, 7= 6.7 Hz, 1H), 4.61 (d,7= 10.1 Hz, 1H), 4.193.95 (m, 1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.27 (d,7=6.3 Hz, 3H), 0.85 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-111.50 (d, 7= 7.3 Hz),112.52 (d, 7= 7.1 Hz),116.50.
315
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
292 A A (Thin film) 3363, 2979, 2939, 2838, 1712, 1586, 1477 1H NMR (400 MHz, CDCfi) for both diastereomers of a 1:1 mixture d 7.18 - 7.09 (m, 2H), 7.01 - 6.87 (m, 10H), 5.76 - 5.58 (m,2H), 5.03 (d, J= 5.4 Hz, 1H), 5.01 (d,7= 4.9 Hz, 1H), 5.01 -4.90 (m, 2H), 4.20 - 4.06 (m, 2H), 3.92 (d, J= 2.1 Hz, 3H), 3.89 (d, 7= 2.0 Hz, 3H), 3.81 (d, 7= 1.9 Hz, 3H), 3.80 (d,7= 1.9 Hz, 3H), 1.44 (s, 9H), 1.42 (s, 9H), 1.25 (d,7=6.6 Hz, 3H), 1.23 (d, 7= 6.3 Hz, 3H), 1.17 (d, 7= 7.1 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H).
293 'R' A SR (Thin film) 3364, 2980, 2839, 1712, 1495, 1455 1H NMR (400 MHz, CDCfi) major diastereomer of a 2:1 mixture d 7.15 (dt, 7= 9.6, 3.0 Hz, 1H), 6.93 (td,7= 8.8, 8.2, 3.1 Hz, 1H), 6.896.81 (m, 2H), 6.80-6.68 (m, 2H), 5.84 (dd, 7= 9.6, 6.2 Hz, 1H), 4.98 (s, 1H), 4.86 (d, 7= 9.2 Hz, 1H), 4.244.07 (m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.23 (d, 7= 6.3 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H).
316
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
294 X ESIMS m/z 412 ([M+H]+) 3H NMR (400 MHz, CDCfi) δ 7.19-7.10 (m, 2H), 7.107.07 (m, 4H), 7.03 - 6.98 (m, 1H), 6.98 - 6.92 (m, 1H), 5.76 (dq, J= 10.3,6.1 Hz, 1H), 4.94 (d, 7= 7.9 Hz, 1H), 4.18-4.03 (m, 1H), 3.94 (d, 7= 10.3 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.22 (d,7=6.1 Hz, 3H), 0.76 (d, 7= 7.2 Hz, 3H).
13CNMR(101 MHz, CDCfi) missing one aromatic C signal due to overlap d 172.84, 141.56, 141.27, 138.32, 137.91, 128.87, 128.87, 128.60, 128.34, 127.62, 127.30, 125.06, 124.89, 73.20, 57.91, 53.39, 49.25,28.31,21.46, 21.42, 19.32, 18.01.
295 «x v\'\ A ESIMS m/z 416 ([M+H]+) 3H NMR (400 MHz, CDCfi) 6 7.32-7.21 (m, 5H), 7.21 7.15 (m, 1H), 6.86 (dd,7 = 8.0, 1.7 Hz, 1H), 6.79 (dd,7 = 11.3, 1.6 Hz, 1H), 5.85 5.72 (m, 1H), 5.04-4.94 (m, 1H), 4.39 (d, 7= 10.1 Hz, 1H), 4.14 (p, 7= 7.4, 6.8 Hz, 1H), 2.26 (s, 3H), 1.42 (s, 9H), 1.24 (d, 7= 6.1 Hz, 3H), 0.90-0.81 (m, 3H).
19F NMR (376 MHz, CDCfi) δ-118.88.
317
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
296 X ESIMS m/z 434 ([M+H]+) 1H NMR (400 MHz, CDCR) δ 7.28-7.17 (m, 3H), 6.996.93 (m, 2H), 6.88 (dd,7 = 8.0, 1.7 Hz, 1H), 6.80 (dd,7 = 11.2, 1.6 Hz, 1H), 5.74 (dq, J= 9.9, 6.2 Hz, 1H), 4.98 (d, J= 7.9 Hz, 1H), 4.37 (d, 7= 10.0 Hz, 1H), 4.224.07 (m, 1H), 2.27 (s, 3H), 1.42 (s, 9H), 1.23 (d,7=6.2 Hz, 3H), 0.88 (d, J= 7.5 Hz, 3H). 19F NMR (376 MHz, CDCR) δ-115.62, -118.85.
297 ESIMS m/z 430 ([M+H]+) 1H NMR (400 MHz, CDCR) δ 7.22 (t, J= 8.0 Hz, 1H), 7.19-7.13 (m, 2H), 7.07 (d, 7= 7.9 Hz, 2H), 6.85 (dd, 7= 8.0, 1.8 Hz, 1H), 6.77 (dd,7 = 11.2, 1.6 Hz, 1H), 5.83 5.69 (m, 1H), 5.03 (d,7=8.0 Hz, 1H), 4.35 (d, 7= 10.3 Hz, 1H), 4.19-4.05 (m, 1H), 2.27 (s, 3H), 2.24 (s, 3H), 1.41 (s,9H), 1.23 (d,7 = 6.1 Hz, 3H), 0.86 (d,7= 8.4 Hz, 3H). 19F NMR (376 MHz, CDCR) δ-118.95.
318
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
298 ESIMS m/z 416 ([M+H]+) 3H NMR (400 MHz, CDC13) 6 7.31 -7.22 (m, 4H), 7.227.11 (m, 1H), 7.12-7.02 (m, 2H), 6.91 (dd, J= 9.4, 8.2 Hz, 1H), 5.74 (dq, 7 = 10.1, 6.2 Hz, 1H), 4.92 (d,7=7.9 Hz, 1H), 4.17-4.04 (m, 1H), 3.97 (d, 7= 10.2 Hz, 1H), 2.23 (d, 7= 1.9 Hz, 3H), 1.41 (s,9H), 1.23 (d, 7= 6.2 Hz, 3H), 0.76 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) 6-120.18.
299 X Y ESIMS m/z 464 ([M+H]+) 3H NMR (400 MHz, CDC13) 6 7.23 (dd, 7=8.6, 6.6 Hz, 1H), 7.07 - 7.01 (m, 2H), 6.88 (t, 7=9.3 Hz, 1H), 6.60 (td, 7= 8.3, 2.6 Hz, 1H), 6.54 (dd, 7= 10.9, 2.5 Hz, 1H), 5.72 (dq, 7=11.8, 6.0 Hz, 1H), 4.95 (d, 7= 8.0 Hz, 1H), 4.44 (d, 7= 10.3 Hz, 1H), 4.19-4.07 (m, 1H), 3.78 (s, 3H), 2.22 (d, 7= 1.9 Hz, 3H), 1.42 (s, 9H), 1.20 (d, 7= 6.1 Hz, 3H), 0.86 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) 6-113.49, -120.41.
319
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
300 sc γ ESIMS m/z 448 ([M+H]+) 3H NMR (400 MHz, CDCh) 6 7.24 (dd, 7=9.6, 5.6 Hz, 1H), 7.16 (t, 7= 7.9 Hz, 1H), 6.85 (dt, 7= 10.4, 2.4 Hz, 3H), 6.79 (dt, 7= 11.3, 1.1 Hz, 1H), 5.70 (dq, 7 = 10.2, 6.2 Hz, 1H), 4.99 (d,7=8.0 Hz, 1H), 4.61 (d, 7= 10.1 Hz, 1H), 4.22 - 4.09 (m, 1H), 2.39 (s, 3H), 2.26 (s, 3H), 1.42 (s, 9H), 1.25 (d,7 = 6.1 Hz, 3H), 0.92 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-116.47, -118.10.
301 sc Ά ESIMS m/z 452 ([M+H]+) 3H NMR (400 MHz, CDCh) 6 7.30-7.21 (m, 2H), 6.926.85 (m, 1H), 6.85-6.74 (m, 3H), 5.84-5.73 (m, 1H), 4.97 (d, 7= 7.9 Hz, 1H), 4.68 (d, 7= 10.0 Hz, 1H), 4.224.07 (m, 1H), 2.28 (s, 3H), 1.42 (s, 9H), 1.26 (d,7=6.2 Hz, 3H), 0.90 (d, 7= 7.3 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-111.63 (d, 7= 7.5 Hz),112.07 (d, 7= 7.0 Hz), 118.16.
320
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
302 γ (Thin film) 3366, 2979, 2932, 1713, 1496, 1452, 1365, 1306, 1248, 1211, 1165, 1053, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C24H32NO4, 398.2326; found, 398.2328 1H NMR (400 MHz, CDC13) 6 7.29-7.21 (m, 4H), 7.197.13 (m, 3H), 7.09 (d,7=7.9 Hz, 2H), 5.77 (dq, 7= 10.3, 6.1Hz, 1H), 4.92 (d,7=7.9 Hz, 1H), 4.17-4.04 (m, 1H), 3.99 (d, 7= 10.3 Hz, 1H), 2.28 (s, 3H), 1.41 (s, 9H), 1.23 (d, 7= 6.1 Hz, 3H), 0.75 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDC13) δ 172.83, 154.94, 141.81, 138.26, 136.50, 129.98, 129.46, 128.47, 127.93 (d, 7= 3.6 Hz), 126.56, 120.94, 79.63, 73.17, 57.62, 49.18, 34.67, 28.31, 20.97, 19.30, 18.00.
303 (Thin film) 3371,2978, 2931, 1712, 1495, 1451, 1365, 1165, 1051,699 HRMS-ESI (m/z) ([M+H]+) calcd for C24H32NO4, 398.2326; found, 398.2324 1H NMR (400 MHz, CDC13) 6 7.26 (d, 7= 4.5 Hz, 5H), 7.18 (d, 7= 7.9 Hz, 2H), 7.05 (d, 7= 7.9 Hz, 2H), 5.77 (dq, 7= 10.0, 6.2 Hz, 1H), 4.94 (d, 7= 7.9 Hz, 1H), 4.18 4.05 (m, 1H), 3.99 (d,7= 10.0 Hz, 1H), 2.26 (s, 3H), 1.42 (s, 9H), 1.22 (d,7=6.2 Hz, 3H), 0.80 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDC13) δ 172.83, 154.94, 141.52, 138.41, 136.15, 129.12, 128.73, 128.21, 128.05, 127.95, 126.79, 124.35, 79.63, 73.17, 57.47, 49.21, 34.67, 28.31, 20.94, 19.30, 18.08.
321
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
304 SS X A (Thin film) 3371,2979, 2932, 1712, 1508, 1452, 1366, 1222, 1160, 1053, 816 HRMS-ESI (m/z) ([M+Na]+) calcd for CiAoFNCUNa, 438.2051; found, 438.2052 1H NMR (400 MHz, CDC13) δ 7.25 - 7.20 (m, 2H), 7.15 (d, 7= 8.1 Hz, 2H), 7.07 (d, J= 7.9 Hz, 2H), 6.96 (t, J= 8.7 Hz, 2H), 5.72 (dq,7 = 9.7, 6.2 Hz, 1H), 4.93 (d,7 = 7.9 Hz, 1H), 4.17-4.06 (m, 1H), 3.99 (d, 7= 9.8 Hz, 1H), 2.27 (s, 3H), 1.42 (s, 9H), 1.21 (d, 7= 6.2 Hz, 3H), 0.81 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.80, 161.65 (d, 7= 245.5 Hz), 154.94, 138.13, 137.32 (d, 7= 3.2 Hz), 136.35, 129.52 (d, 7 = 7.9 Hz), 129.22, 127.89, 126.12 (d, 7= 7.8 Hz), 115.56 (d, 7= 21.3 Hz), 79.68, 73.01, 56.60, 49.19, 34.67, 31.59, 28.31, 20.95, 19.22, 18.07.
322
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
305 X AN ¥ (Thin film) 3371,2979, 2933, 1710, 1509, 1452, 1366, 1222, 1160, 1051, 699 ESIMS m/z 402.2 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 7.31 -7.23 (m, 7H), 6.986.92 (m, 2H), 5.75 (dq,/ = 10.0, 6.2 Hz, 1H), 4.91 (d,/ = 7.8 Hz, 1H), 4.18-4.07 (m, 1H), 4.02 (d,/= 10.0 Hz, 1H), 1.42 (s, 9H), 1.23 (d,/= 6.2 Hz, 3H), 0.83 (d, /= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.80, 161.61 (d, /= 245.2 Hz), 154.93, 141.02, 137.26 (d,/= 3.4 Hz), 129.55 (d,/= 7.9 Hz), 128.86, 127.99, 127.05, 115.29 (d,/= 21.2 Hz), 79.74, 73.05, 57.10, 49.18, 34.67, 28.31, 19.29, 18.12.
323
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
306 as Γ3 (Thin film) 3371,2979, 2932, 1712, 1509, 1452, 1366, 1222, 1161, 1052, 815 ESIMS m/z 438.2 ([M+Na]+) 1H NMR (400 MHz, CDCh) 6 7.26-7.21 (m, 2H), 7.14 (d, 7= 8.2 Hz, 2H), 7.09 (d, 7= 8.1 Hz, 2H), 6.98-6.90 (m,2H), 5.73 (dq,7=10.2, 6.1Hz, 1H), 4.91 (d,7=8.0 Hz, 1H), 4.17-4.06 (m, 1H), 3.98 (d, 7= 10.2 Hz, 1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.1 Hz, 3H), 0.82 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.80, 161.56 (d, 7= 245.0 Hz), 154.93, 138.04, 137.58 (d, 7= 3.3 Hz), 136.69, 129.54, 129.43 (d, 7= 7.8 Hz), 127.82, 115.25 (d, 7= 21.2 Hz), 79.72, 73.11, 56.76, 49.18, 34.67, 28.31, 20.97, 19.28, 18.12.
324
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
307 A CN k ''N (Thin film) 3370, 2980, 2936, 1712, 1503, 1453, 1366, 1164, 1053, 966, 851, 698 HRMS-ESI (m/z) ([M+H]+) calcd for C23H28F2NO4, 420.1981; found, 420.1995 1H NMR (400 MHz, CDCI3) δ 7.33 - 7.24 (m, 5H), 7.22 7.14 (m, 1H), 6.86-6.73 (m, 2H), 5.84-5.72 (m, 1H), 4.90 (d, J= 8.0 Hz, 1H), 4.40 (d, 7= 10.2 Hz, 1H), 4.18 4.05 (m, 1H), 1.42 (s, 9H), 1.26 (d, J= 6.1 Hz, 3H), 0.78 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.74, 162.98161.09 (m), 160.06 (dd,7 = 169.5, 12.1 Hz), 154.93, 140.15, 129.79, 128.61, 128.22, 127.00, 124.39 (d, 7 = 18.6 Hz), 111.62 (d,7 = 19.5 Hz), 104.70- 103.41 (m), 79.71, 72.30, 49.40, 49.15, 34.67, 28.31, 18.97, 17.99.
325
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
308 A SN A (Thin film) 3364, 2980, 2933, 1713, 1502, 1453, 1366, 1164, 1053, 966, 850 HRMS-ESI (m/z) ([M+Na]+) calcd for C24H29F2NO4Na, 456.1957; found, 456.1953 3H NMR (400 MHz, CDCf) δ 7.25 - 7.20 (m, 1H), 7.18 (d, 7= 8.1 Hz, 2H), 7.07 (d, 7= 7.6 Hz, 2H), 6.85 - 6.72 (m,2H), 5.76 (dtd,7= 9.5, 6.8, 5.5 Hz, 1H), 4-92 (d,7 = 7.8 Hz, 1H), 4.36 (d, 7= 10.0 Hz, 1H), 4.19-4.01 (m, 1H), 2.27 (s, 3H), 1.42 (s, 9H), 1.25 (d, 7= 6.2 Hz, 3H), 0.82 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCf) δ 172.74, 161.98 (dd, 7= 167.8, 11.9 Hz), 160.01 (dd, 7 = 167.8, 11.9 Hz), 154.93, 137.05, 136.57, 129.90, 129.24, 128.11, 124.66 (d, 7= 11.5 Hz), 111.57 (d, 7= 20.4 Hz), 104.69- 102.95 (m), 79.70, 72.38, 49.18, 48.94, 28.31, 20.97, 18.97, 18.07.
326
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
309 ''N Y (Thin film) 3364, 2981, 1711, 1604, 1502, 1454, 1380, 1366, 1224, 1161, 1053, 966, 851, HRMS-ESI (m/z) ([M+Na]+) calcd for C23H26F3NO4Na, 460.1706; found, 460.1712 1H NMR (400 MHz, CDC13) δ 7.29-7.19 (m, 3H), 6.996.93 (m,2H), 6.86-6.75 (m, 2H), 5.81 - 5.70 (m, 1H), 4.90 (d, J= 7.9 Hz, 1H), 4.37 (d, 7= 10.1 Hz, 1H), 4.214.06 (m, 1H), 1.42 (s, 9H), 1.26 (d, J= 6.2 Hz, 3H), 0.85 (dd,7=7.8, 1.1 Hz, 3H). 13CNMR(126 MHz, CDC13) δ 172.71, 162.85, 162.71, 161.37, 161.28, 160.87, 160.75, 159.39, 159.30, 154.93, 135.92, 129.76 (d, 7= 7.7 Hz), 115.44 (d, 7= 21.3 Hz), 111.71 (d,7= 18.0 Hz), 104.71 - 103.96 (m), 79.80, 72.20, 49.16, 48.78, 34.67, 28.30, 18.99, 18.09.
310 vS HRMS-ESI (m/z) ([M+H]+) calcd for C26H38NO2, 396.2897; found, 396.2896
311 Y NS HRMS-ESI (m/z) ([M+H]+) calcd for C24H34NO2, 368.2584; found, 368.2584 'H NMR (400 MHz, Acetone-d6) δ 7.31 -7.21 (m,4H), 7.15 (ddd, 7= 10.9, 8.5, 2.5 Hz, 4H), 5.87 (dq,7 = 10.0, 6.0 Hz, 1H), 4.05 (d, 7= 10.5 Hz, 1H), 3.85 (q,7= 7.2 Hz, 1H), 3.31 (dt,7= 3.3, 1.7 Hz, 3H), 2.91-2.73 (m,2H), 1.26 (d, 7= 6.1 Hz, 3H), 1.19 (t, 7= 6.7 Hz, 12H), 0.81 (dd, 7= 7.3, 2.8 Hz, 3H).
327
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
312 A'\ o iCS: HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO2, 340.2271; found, 340.2273
313 ko OS o iCS: HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO2, 348.1770; found, 348.1780 'η NMR (400 MHz, Acetone-d6) δ 7.34 (dd, J = 8.7, 5.7 Hz, 1Η), 7.26 (dd,7 = 8.7, 5.8 Hz, 1H), 7.026.80 (m, 5H), 5.75 (dq,7 = 9.8, 6.1 Hz, 1Η), 4.59 (d,7 = 9.8 Hz, 1H), 3.96 (q,7=7.2 Hz, 1H), 3.72-3.60 (m, 2H), 2.40 (s, 3H), 2.37 (s, 3H), 1.34 (d, 7= 6.2 Hz, 3H), 1.03 (d, 7= 7.3 Hz, 3H). 19FNMR(376 MHz, Acetone) δ-119.66, -120.05.
314 A'\ Y OS iCS: ESIMS m/z 320 ([M+H]+)
315 γ OS X >'V ESIMS m/z 320 ([M+H]+)
316 Y A ESIMS m/z 380.5 ([M+H]+)
317 O' ESIMS m/z 374.4 ([M+H]+)
328
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
318 ?? Y SN ESIMS m/z 298 ([M+H]+)
319 Ύ Y ESIMS m/z 334 ([M+H]+)
320 'S ESIMS m/z 420 ([M+H]+)
321 ESIMS m/z 428 ([M+H]+)
322 Ά. > (Thin film) 2851, 1740, 1494, 1451, 1253, 1231, 1204, 1117, 1080, 1046, 871, 746, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C18H22NO2, 284.1645; found, 284.1644
323 ESIMS m/z 412.3 ([M+H]+)
324 v\'\ C/ SN ESIMS m/z 408.4 ([M+H]+)
325 Y ESIMS m/z 440.3 ([M+H]+)
326 ESIMS m/z 400.4 ([M+H]+)
329
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
327 A 'S AS; ESIMS m/z 404 ([M+H]+)
328 A ESIMS m/z 372 ([M+H]+)
329 y ESIMS m/z 372 ([M+H]+)
330 A ESIMS m/z 380 ([M+H]+)
331 A ESIMS m/z 380 ([M+H]+)
332 y cs A HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO4, 380.1668; found, 380.1649 3H NMR (500 MHz, Methanol-d4) δ 6.74 (dddd, J = 17.6, 8.0,3.7, 1.8 Hz, 4H), 6.58 (ddt, J= 12.2, 10.0, 2.3 Hz, 2H), 5.83 (dq, 7 = 10.2, 6.1Hz, 1H), 4.13 (d,7= 10.3 Hz, 1H), 3.93 (q, 7= 7.2 Hz, 1H), 3.78 (s, 3H), 3.77 (s, 3H), 1.28 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.3 Hz, 3H) (NH protons not observed). 19FNMR(471 MHz, Methanol-d4) δ -112.85 (t, 7 = 10.0 Hz),-113.22 (t, 7 = 10.3 Hz).
330
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
333 A X OS A HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO6, 404.2068; found, 404.2038 3H NMR (500 MHz, Methanol-d4) δ 6.51 (dd, J= 5.2.2.3 Hz, 4H), 6.35 (dt, J = 13.0, 2.2 Hz, 2H), 5.82 (dq, 7= 10.4, 6.1 Hz, 1H), 3.99 (d, 7= 10.4 Hz, 1H), 3.89 (q, J= 7.2 Hz, 1H), 3.75 (s, 6H), 3.74 (s, 6H), 1.27 (d, J= 6.2 Hz, 3H), 0.96 (d,7= 7.3 Hz, 3H) (NH protons not observed).
334 os HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO4, 372.2169; found, 372.2146 3H NMR (500 MHz, Methanol-d4) δ 6.75 (d, J= 4.0 Hz, 2H), 6.69 (dt,7= 6.6, 1.9 Hz, 2H), 6.61 (s, 1H), 6.58 (d, J= 2.3 Hz, 1H), 5.82 (dq, 7=10.4, 6.1 Hz, 1H), 3.97 (d, J= 10.5 Hz, 1H), 3.85 (q, 7= 7.3 Hz, 1H), 3.75 (s, 3H), 3.74 (s, 3H), 2.29 (s, 3H), 2.27 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 0.92 (d, 7= 7.2 Hz, 3H) (NH protons not observed).
335 a eS os X HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO4, 372.2169; found, 372.2146 3H NMR (500 MHz, Methanol-d4) δ 6.75 (d, 7= 4.0 Hz, 2H), 6.69 (dt,7= 6.6, 1.9 Hz, 2H), 6.61 (s, 1H), 6.58 (d, 7= 2.3 Hz, 1H), 5.82 (dq, 7=10.4, 6.1 Hz, 1H), 3.97 (d, 7= 10.5 Hz, 1H), 3.85 (q, 7= 7.3 Hz, 1H), 3.75 (s, 3H), 3.74 (s, 3H), 2.29 (s, 3H), 2.27 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 0.92 (d, 7= 7.2 Hz, 3H) (NH protons not observed).
331
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
336 OS ESIMS m/z 372.1 ([M+H]+) 3H NMR (500 MHz, Methanol-d4) δ 7.03 (dd, J= 11.9, 7.5 Hz, 2H), 6.926.80 (m, 4H), 5.88 (dq,7 = 10.5, 6.1Hz, 1H), 4.05 (d,7 = 10.4 Hz, 1H), 3.88 (q, 7= 7.2 Hz, 1H), 3.80 (d,7= 1.0 Hz, 6H), 2.12 (s, 3H), 2.11 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H) (NH protons not observed).
337 ''S OS ;'S HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO4, 380.1668; found, 380.1667 XH NMR (500 MHz, Methanol-d4) δ 7.15 - 7.06 (m,4H), 7.03 (q, 7= 8.5 Hz, 2H), 5.77 (dq, 7= 10.1,6.2 Hz, 1H), 4.06 (d, 7 = 10.0 Hz, 1H), 3.93 (q, 7= 7.3 Hz, 1H), 3.83 (s, 3H), 3.82 (s, 3H), 1.25 (d, 7= 6.1 Hz, 3H), 1.00 (d, 7= 7.3 Hz, 3H) (NH protons not observed). 19FNMR(471 MHz, Methanol-d4) δ -136.28 (dd, 7=12.6, 8.5 Hz),-136.53 (dd, 7 = 12.6, 8.9 Hz).
338 $0 ESIMS m/z 372.1 ([M+H]+) 3H NMR (500 MHz, Methanol-d4) δ 7.14 - 7.03 (m, 4H), 6.80 (dd,7= 12.7, 8.4 Hz, 2H), 5.77 (dq,7 = 10.3, 6.2 Hz, 1H), 3.92 (d,7 = 10.4 Hz, 1H), 3.86 (q,7= 7.2 Hz, 1H), 3.78 (s, 3H), 3.76 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.23 (d,7=6.1 Hz, 3H), 0.92 (d, 7= 7.3 Hz, 3H) (NH protons not observed).
332
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
339 SR QS HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO6, 404.2068; found, 404.2059 3H NMR (500 MHz, Methanol-d4) δ 7.03 (d, J= 3.0 Hz, 1H), 6.90-6.80 (m, 3H), 6.75 (ddd, J= 8.9, 4.5, 3.1Hz, 2H), 5.99 (dq,7 = 10.2, 6.2 Hz, 1H), 4.91 (d,7 = 10.2 Hz, 1H), 3.89 (q,7= 7.2 Hz, 1H), 3.81 (s, 3H), 3.73 (s, 3H), 3.73 (s, 3H), 3.70 (s, 3H), 1.24 (d, 7=6.2 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H) (NH protons not observed).
340 A QS (Thin film) 2938, 1742, 1617, 1501, 1473, 1429, 1293, 1233, 1189, 1119, 1050, 950, 785 HRMS-ESI (m/z) ([M+H]+) calcd for C20H22F4NO4, 416.1479; found, 416.1479
341 vQ QS SS A (Thin film) 2866, 1742, 1500, 1454, 1378, 1226, 1113, 1048, 808, 792, 737 HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO2, 340.2271; found, 340.2269
342 S' RS QS SR (Thin film) 2863, 1748, 1736, 1526, 1500, 1456, 1376, 1238, 1187, 1116, 1048, 810, 791, 751 HRMS-ESI (m/z) ([M+H]+) calcd for C22H30NO2, 340.2271; found, 340.2274
333
2019201931 20 Mar 2019
Cmpd. No. 1 eg. D MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
343 (Thin film) 2878, 1751, 1738, 1587, 1526, 1494, 1459, 1240, 1226, 1188, 1130, 1048, 811, 754 HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO2, 348.1770; found, 348.1771
344 x> A (Thin film) 2962, 1747, 1596, 1497, 1234, 1205, 1114, 1052, 1034, 829, 811, 713 HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO4, 380.1668; found, 380.1665
345 x> X X (Thin film) 2839, 1744, 1622, 1583, 1506, 1444, 1287, 1254, 1193, 1116, 1050, 1030, 872, 833 HRMS-ESI (m/z) ([M+H]+) calcd for C20H24F2NO4, 380.1668; found, 380.1671
346 x> X X (Thin film) 2941, 1742, 1615, 1588, 1457, 1417, 1326, 1241, 1171, 1116, 1032, 873, 859, 740 HRMS-ESI (m/z) ([M+H]+) calcd for C22H24F6NO4, 480.1604; found, 480.1607
347 'X k 'k ESIMS m/z 408.2 ([M+H]+)
334
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
348 & A ESIMS m/z 436.2 ([M+H]+)
349 «X ESIMS m/z 404.1 ([M+H]+)
350 Ύ ESIMS m/z 372.1 ([M+H]+)
351 ex > ESIMS m/z 372.1 ([M+H]+)
352 I ESIMS m/z 380 ([M+H]+)
353 X A'\ >'V a ESIMS m/z 372 ([M+H]+)
354 A H ESIMS m/z 332 ([M+H]+)
355 s>\\ A A ESIMS m/z 316 ([M+H]+)
356 ''k ESIMS m/z 332 ([M+H]+)
357 ESIMS m/z 316 ([M+H]+)
335
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
358 X Γ3 AS: ESIMS m/z 346 ([M+H]+)
359 •-γχ AN A' sX ESIMS m/z 330 ([M+H]+)
360 V. X ESIMS m/z 346 ([M+H]+)
361 ESIMS m/z 350 ([M+H]+)
362 X ESIMS m/z 334 ([M+H]+)
363 X v\'\ ap as AS ESIMS m/z 350 ([M+H]+)
364 X A' ESIMS m/z 334 ([M+H]+)
365 >x\ V. X ESIMS m/z 312([M+H]+)
366 a iv3 iv3 ESIMS m/z 364.2 ([M+H]+)
367 X ESIMS m/z 368.2 ([M+H]+)
336
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
368 NS ESIMS m/z 364.2 ([M+H]+)
369 NS Y ESIMS m/z 352.2 ([M+H]+)
370 Y NS X ESIMS m/z 316([M+H]+)
371 NS ESIMS m/z 334([M+H]+)
372 \S- ESIMS m/z 330 ([M+H]+)
373 A'\ ss SN Y SN ESIMS m/z 348([M+H]+)
374 ss X X ESIMS m/z 352 ([M+H]+)
375 SN Y ESIMS m/z 316 ([M+H]+)
376 S\ ''N SN ESIMS m/z 364 ([M+H]+)
337
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
377 A (Thin film) 3408, 2920, 1740, 1512, 1495, 1452, 1232, 1198, 1114, 1048, 734, 699 HRMS-ESI (m/z) ([M+H]+) calcd for c19h24no2, 298.1802; found, 298.1798
378 A'\ «X X γ (Thin film) 2877, 1749, 1599, 1515, 1493, 1452, 1228, 1193, 1139, 1119, 1055, 744, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C19H24NO2, 298.1802; found, 298.1795
379 A > (Thin film) 2879, 1747, 1602, 1508, 1454, 1227, 1197, 1116, 1053, 814, 733 HRMS-ESI (m/z) ([M+H]+) calcd for C19H23FNO2, 316.1707; found, 316.1703
380 X (Thin film) 2896, 1741, 1604, 1509, 1453, 1226, 1117, 1047, 732, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C18H21FNO2, 302.1551; found, 302.1548
381 (Thin film) 2919, 1741, 1603, 1509, 1459, 1229, 1117, 1049, 813 HRMS-ESI (m/z) ([M+H]+) calcd for C19H23FNO2, 316.1707; found, 316.1705
338
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
382 SN (Thin film) 3396, 2936, 1743, 1619, 1602, 1503, 1454, 1235, 1208, 1145, 1116, 966, 850, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C18H20F2NO2, 320.1457; found, 320.1451
383 A (Thin film) 3440, 2924, 1743, 1603, 1502, 1234, 1208, 1116, 1100, 1083, 966, 849 HRMS-ESI (m/z) ([M+H]+) calcd for C19H22F2NO2, 334.1613; found, 334.1606
384 SN A A (Thin film) 3384, 2935, 1743, 1603, 1503, 1228, 1117, 966, 850 HRMS-ESI (m/z) ([M+H]+) calcd for C18H19F3NO2, 338.1362; found, 338.1356
385 SN Ύ A (Thin film) 3384, 2935, 1743, 1603, 1503, 1228, 1117, 966, 850 HRMS-ESI (m/z) ([M+H]+) calcd for C18H19F3NO2, 338.1362; found, 338.1356
339
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
386 A A > HRMS-ESI (m/z) ([M+H]+) calcd for C25H25F2N2O5, 471.1728; found, 471.1726. XH NMR (400 MHz, CDC13) δ 12.05 (d, 7= 0.6 Hz, 1H), 8.31 (d, 7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.22 (dddd, 7= 11.7, 8.5, 5.3,2.6 Hz, 4H), 7.02-6.89 (m, 4H), 6.86 (d, 7= 5.2 Hz, 1H), 5.72 (dq,J = 9.7, 6.2 Hz, 1H), 4.60 - 4.46 (m, 1H), 4.05 (d, 7= 9.8 Hz, 1H), 3.94 (s, 3H), 1.24 (d,7 = 6.2 Hz, 3H), 1.06 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 171.56, 168.60, 162.98, 162.87, 160.54, 160.42, 155.41, 148.75, 140.43, 136.83, 136.80, 136.73, 136.70, 130.36, 129.54, 129.46, 115.83, 115.62, 115.50, 115.29, 109.46, 73.32, 56.14, 56.08, 47.87,30.92, 19.12, 17.67.
340
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
387 ¥ AN HRMS-ESI (m/z) ([M+H]+) calcd for C25H25F2N2O5, 471.1723; found, 471.1726. 1H NMR (400 MHz, CDCh) δ 12.08 (d,/= 0.7 Hz, 1H), 8.20 (d,/= 8.0 Hz, 1H), 7.99 (d,/= 5.2 Hz, 1H), 7.247.13 (m,4H), 7.03 -6.93 (m, 2H), 6.93 - 6.84 (m, 3H), 5.69 (dq,/= 9.1, 6.2 Hz, 1H), 4.59-4.45 (m, 1H), 4.05 (d,/= 9.0 Hz, 1H), 3.96 (s, 3H), 1.34 (d, J = 7.2 Hz, 3H), 1.22 (d,/= 6.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 171.26, 168.55, 162.94, 162.84, 160.49, 160.40, 155.44, 148.78, 140.44, 136.82, 136.79, 136.46, 136.43, 130.35, 129.74, 129.67, 129.65, 129.57, 115.76, 115.55, 115.46, 115.24, 109.50, 99.99, 73.34,56.11,55.66, 47.80, 18.95, 17.74.
341
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
388 ec (Thin film) 3371,2981, 1735, 1649, 1495, 1261, 954, 800, 728 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O5, 499.2039; found, 499.2044 1H NMR (500 MHz, CDCh) 612.05 (s, 1H), 8.32 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.24 (dd,7=8.7, 5.8 Hz, 1H), 7.14 (dd, J= 8.6, 5.8 Hz, 1H), 6.92-6.72 (m, 5H), 5.64 (dq,7=9.8, 6.2 Hz, 1H), 4.53 (p,7=7.3 Hz, 1H), 4.44 (d, 7= 9.7 Hz, 1H), 3.94 (s, 3H), 2.38 (s, 3H),2.31 (s, 3H), 1.31 (d,7 = 6.1 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H). 19F NMR (471 MHz, CDCh) δ-116.46 (td, 7= 8.8, 5.7 Hz),-116.87 (td, 7= 9.0, 5.9 Hz).
389 (Thin film) 3370, 2962, 1735, 1649, 1527, 1264, 1145, 801, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C33H43N2O5, 547.3166; found, 547.3163 1H NMR (500 MHz, CDCh) δ 12.12 (s, 1H), 8.38 (d, 7= 7.9 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.29 (d, 7= 8.3 Hz, 2H), 7.25 (s, 6H), 6.86 (d,7 = 5.2 Hz, 1H), 5.80 (dq,7= 10.3, 6.2 Hz, 1H), 4.48 (p, 7 = 7.3 Hz, 1H), 3.98 (d,7= 10.3 Hz, 1H), 3.93 (s, 3H), 1.28- 1.25 (m, 12H), 1.24 (s, 9H), 0.83 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.76, 168.50, 155.32, 149.63, 149.44, 148.70, 140.42, 138.71, 138.13, 130.51, 127.66, 127.63, 125.64, 125.36, 109.37, 74.03, 57.25, 56.05, 47.78,34.37,34.32,31.31, 31.30, 19.33, 17.40.
342
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
390 (Thin film) 3370, 2959, 1734, 1649, 1527, 1450, 1280, 1145, 1045, 801, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C31H39N2O5, 519.2853; found, 519.2848 1H NMR (500 MHz, CDCf) δ 12.12 (s, 1H), 7.98 (d,7= 5.2 Hz, 1H), 7.23 (dd,7= 8.3, 2.6 Hz, 5H), 7.13 (d,7= 7.9 Hz, 2H), 7.09 (d,7=7.9 Hz, 2H), 6.86 (d, 7= 5.2 Hz, 1H), 5.80 (dq, 7=10.4, 6.1 Hz, 1H), 4.49 (p, 7= 7.3 Hz, 1H), 3.98 (d, 7= 10.2 Hz, 1H), 3.93 (s, 3H), 2.82 (tp, 7 = 13.9, 6.9 Hz, 2H), 1.25 (d, 7= 6.1 Hz, 3H), 1.20 (d,7= 6.9 Hz, 6H), 1.16 (d, 7= 6.9 Hz, 6H), 0.86 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 171.75, 168.50, 155.32, 148.70, 147.36, 147.20, 140.41, 139.09, 138.58, 130.51, 127.91, 126.79, 126.50, 109.37, 73.97, 57.39, 56.05,47.80, 33.64,33.62, 23.98, 23.97, 23.93, 19.31, 17.45.
343
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
391 1 (Thin film) 3370, 2959, 1734, 1649, 1576, 1450, 1262, 1147, 1050, 800, 728 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O5, 491.2540; found, 491.2540 1H NMR (500 MHz, CDC13) δ 12.12 (s, 1H), 8.36 (d, J= 7.9 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.07-6.89 (m, 6H), 6.86 (d, 7= 5.3 Hz, 1H), 5.76 (dq, 7= 10.3,6.1 Hz, 1H), 4.52 (p, 7= 7.3 Hz, 1H), 3.94 (s, 3H), 3.91 (d,7 = 10.3 Hz, 1H), 2.17 (dd, 7 = 20.2, 12.3 Hz, 12H), 1.24 (d, 7= 6.1 Hz, 3H), 0.99 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 171.72, 168.48, 155.32, 148.69, 140.38, 139.15, 138.98, 136.84, 136.38, 135.01, 134.59, 130.50, 129.93, 129.62, 129.33, 129.28, 125.27, 124.99, 109.35, 73.76, 57.12, 56.05,47.88, 19.88, 19.79, 19.30, 19.29, 19.24, 17.67.
392 A (Thin film) 3358, 2936, 1749, 1659, 1508, 1223, 1131 HRMS-ESI (m/z) ([M+H]+) calcd for C25H22F5N2O5, 525.1443; found, 525.1451 1H NMR (400 MHz, CDCI3) δ 11.51 - 11.26 (m, 1H), 8.72-8.46 (m, 1H), 8.10 7.95 (m, 1H), 7.24-7.13 (m, 4H), 7.03 - 6.82 (m, 5H), 5.88-5.70 (m, 1H), 5.31 5.11 (m, 1H), 4.12-4.04 (m, 1H), 4.01-3.93 (m, 3H), 1.32- 1.25 (m, 3H).
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
393 A (Thin film) 3371,2939, 1734, 1649, 1599, 1500, 1277, 1150, 1034, 953 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1926 3H NMR (300 MHz, CDCf) δ 12.11 (d, 7= 0.7 Hz, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.3 Hz, 1H), 7.35 (dd, 7=8.5, 6.7 Hz, 1H), 7.257.08 (m, 1H), 6.86 (d,7=5.2 Hz, 1H), 6.61-6.45 (m, 4H), 5.89 (dq, 7= 9.6, 6.1 Hz, 1H), 4.83 (d, 7= 9.7 Hz, 1H), 4.71-4.44 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.73 (s, 3H), 1.23 (d,7=6.2 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H).
394 SN HRMS-ESI (m/z) ([M+H]+) calcd for C26H29N2O5, 448.2071; found, 449.2081. 3H NMR (400 MHz, CDCf) δ 12.09 (s, 1H), 8.41 (d,7= 7.9 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.32-7.12 (m, 10H), 6.86 (d, 7= 5.2 Hz, 1H), 5.87 (q, 7= 6.3 Hz, 1H), 4.59 (p, 7= 7.2 Hz, 1H), 3.94 (s, 3H), 1.75 (s, 3H), 1.20- 1.14 (m, 6H). 13CNMR(101 MHz, CDCf) δ 171.61, 168.58, 155.36, 148.74, 146.44, 144.98, 140.40, 130.48, 128.16, 128.10, 127.93, 127.35, 126.33, 126.16, 109.43, 76.21, 56.06, 50.40, 48.00, 23.98, 17.94, 15.94.
345
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
395 ίΎ A (Thin film) 3370, 2981, 1734, 1648, 1575, 1527, 1494, 1480, 1450, 1279, 1262, 1242, 1144, 1047, 909, 729, 702 HRMS-ESI (m/z) ([M+H]+) calcd for C25H27N2O5, 435.1914; found, 435.1924 1:1 mixture of diastereomers. XH NMR (500 MHz, CDCh) δ 12.14 (s, 1H), 12.09 (s, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 8.24 (d, 7= 7.9 Hz, 1H), 8.00 (d, 7= 5.2 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.32-7.17 (m, 9H), 7.16-7.10 (m, 1H), 6.88 (d, 7= 5.2 Hz, 1H), 6.86 (d,7= 5.2 Hz, 1H), 5.88-5.75 (m, 1H), 4.56-4.44 (m, 1H), 4.07 (d, 7= 5.6 Hz, 1H), 4.05 (d, 7= 6.1 Hz, 1H), 3.95 (s, 3H), 3.94 (s, 1H), 1.29 (d,7 = 7.2 Hz, 3H), 1.26 (d,7= 6.2 Hz, 3H), 1.24 (d,7=6.2 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H).
396 S' A (Thin film) 3372, 2985, 2228, 1738, 1649, 1576, 1529, 1504, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C27H25N4O5, 485.1819; found, 485.1824 XH NMR (400 MHz, CDCh) δ 11.96 (s, 1H), 8.24 (d,7= 7.9 Hz, 1H), 7.98 (t,7=5.4 Hz, 1H), 7.63 -7.59 (m, 2H), 7.57-7.50 (m, 2H), 7.40 - 7.37 (m,2H), 7.377.33 (m,2H), 6.93 -6.84 (m, 1H), 5.83 - 5.71 (m, 1H), 4.61-4.46 (m, 1H), 4.21 (d, 7= 9.3 Hz, 1H), 3.96 (s, 3H), 1.28 (d,7=6.1 Hz, 3H), 1.13 (d, 7= 7.2 Hz, 3H).
346
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Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
397 a (Thin film) 2984, 1739, 1681, 1617, 1577, 1530, 1482 HRMS-ESI (m/z) ([M+H]+) calcd for C27H25F6N2O5, 571.1662; found, 571.1671 1H NMR (400 MHz, CDC13) δ 12.01 (s, 1H), 8.31 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.57 (d, J= 8.1 Hz, 2H), 7.52 (d, 7= 8.3 Hz, 2H), 7.42 (d, 7= 8.3 Hz, 2H), 7.39 (d, 7= 8.3 Hz, 2H), 6.87 (d, 7= 5.3 Hz, 1H), 5.90-5.82 (m, 1H), 4.59 - 4.48 (m, 1H), 4.22 (d, 7= 9.6 Hz, 1H), 3.94 (s, 3H), 1.29 (d, 7= 6.2 Hz, 3H), 1.03 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ -62.66, -62.69.
398 (Thin film) 3364, 2981, 1713, 1650, 1607, 1529, 1481, 1418 HRMS-ESI (m/z) ([M+H]+) calcd for C31H35N2O9, 579.2337; found, 579.2349 1H NMR (400 MHz, CDCI3) δ 12.03 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 8.00 - 7.95 (m, 3H), 7.93 (d, 7= 8.4 Hz, 2H), 7.38 (d, 7= 8.4 Hz, 2H), 7.35 (d, 7= 8.3 Hz, 2H), 6.86 (d, 7= 5.2 Hz, 1H), 5.86 (dp, 7= 9.1, 7.1, 6.6 Hz, 1H), 4.60-4.50 (m, 1H), 4.35 (qd, 7= 7.1, 2.8 Hz, 4H), 4.22 (d, 7= 9.7 Hz, 1H), 3.93 (s, 3H), 1.37 (t, 7 = 7.2 Hz, 3H), 1.37 (t, 7= 7.1 Hz, 3H), 1.28 (d, 7= 6.2 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H).
347
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
399 > (Thin film) 3364, 2939, 1734, 1649, 1488, 1449, 1243 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29CI2N2O7, 563.1346; found, 563.1354 1H NMR (400 MHz, CDCh) δ 12.10 (s, 1H), 8.34 (d,/= 7.9 Hz, 1H), 7.96 (d,/= 5.2 Hz, 1H), 7.32 (d,/= 8.3 Hz, 1H), 7.09 (d,/= 8.7 Hz, 1H), 6.86 (d,/= 5.3 Hz, 1H), 6.85 - 6.80 (m, 3H), 6.74 (d,/= 2.0 Hz, 1H), 5.88 (dq,/= 9.6, 6.2 Hz, 1H), 4.83 (d,/= 9.7 Hz, 1H), 4.54 (p,/= 7.2 Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 1.23 (d,/= 6.2 Hz, 3H), 1.11 (d,/= 7.2 Hz, 3H).
400 X if (Thin film) 3373, 2980, 1734, 1649, 1598, 1480, 1263, 1161, 1040 HRMS-ESI (m/z) ([M+H]+) calcd for C29H33F2N2O7, 559.225; found, 559.2258 3H NMR (400 MHz, CDCh) δ 12.12 (s, 1H), 8.36 (d,/= 7.9 Hz, 1H), 7.96 (d,/= 5.2 Hz, 1H), 7.32 (dd,/= 8.5, 6.8 Hz, 1H), 7.15 (dd,/= 9.0,6.9 Hz, 1H), 6.85 (d,/= 5.2 Hz, 1H), 6.62-6.39 (m, 4H), 5.99-5.89 (m, 1H), 4.82 (d,/= 10.1 Hz, 1H), 4.55 (p,/= 7.2 Hz, 1H), 4.03 -3.81 (m, 7H), 1.47 (t,/ = 7.0 Hz, 3H), 1.40 (t,/= 7.0 Hz, 3H), 1.24 (d,/= 6.1 Hz, 3H), 1.10 (d,/= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.62,-114.03.
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
401 SR QR A (Thin film) 3367, 2980, 1735, 1650, 1576, 1528, 1243, 1147, 1041 HRMS-ESI (m/z) ([M+H]+) calcd for C29H33CI2N2O7, 591.1659; found, 591.1662 1H NMR (400 MHz, CDCfi) δ 12.10 (s, 1H), 8.36 (d, J= 7.9 Hz, 1H), 7.96 (d,7=5.2 Hz, 1H), 7.29 (d, 7= 8.3 Hz, 1H), 7.11 (d, 7= 8.2 Hz, 1H), 6.85 (d, 7= 5.3 Hz, 1H), 6.80 (dd, 7= 8.2, 2.0 Hz, 2H), 6.77 (d, 7= 2.0 Hz, 1H), 6.70 (d, 7= 2.1 Hz, 1H), 5.92 (dq, 7=10.2, 6.2 Hz, 1H), 4.82 (d, 7 = 10.0 Hz, 1H), 4.62 - 4.47 (m, 1H), 4.03-3.81 (m, 7H), 1.47 (t, 7= 6.9 Hz, 3H), 1.39 (t, 7= 6.9 Hz, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 1.12 (d, 7= 7.2 Hz, 3H).
402 SR QR A (Thin film) 3374, 2976, 1733, 1649, 1527, 1450, 1261, 1142, 1044 HRMS-ESI (m/z) ([M+H]+) calcd for C31H39N2O7, 551.2752; found, 551.2716 1H NMR (400 MHz, CDCfi) δ 12.17 (s, 1H), 8.40 (d,7= 7.9 Hz, 1H), 7.96 (d,7=5.2 Hz, 1H), 7.28 (d, 7= 7.8 Hz, 1H), 7.13 (d, 7= 7.6 Hz, 1H), 6.84 (d, 7= 5.3 Hz, 1H), 6.70-6.50 (m, 4H), 5.96 (dq, 7= 10.4,6.1 Hz, 1H), 4.90 (d,7= 10.2 Hz, 1H), 4.53 (p, 7= 7.2 Hz, 1H), 4.05-3.80 (m, 7H), 2.26 (s, 3H), 2.22 (s, 3H), 1.47 (t, 7= 7.0 Hz, 3H), 1.39 (t, 7= 6.9 Hz, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 1.04 (d,7= 7.2 Hz, 3H).
349
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
403 Y HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1944; found, 531.1937 1H NMR (400 MHz, CDCfi) δ 12.04 (d, 7= 0.7 Hz, 1H), 8.31 (d, 7= 7.9 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.056.90 (m, 2H), 6.90 - 6.77 (m, 5H), 5.73 (dq, 7=10.0, 6.1 Hz, 1H), 4.63 - 4.47 (m, 1H), 3.99 (d, 7= 9.9 Hz, 1H), 3.94 (s, 3H), 3.86 (s, 3H), 3.85 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.08 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCfi) δ-137.02, -137.51.
350
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (Y, 13c, 19f)
404 Y HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2432; found, 523.2426 3H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.20 (d, 7= 8.6 Hz, 1H), 7.16-7.08 (m, 1H), 6.86 (d, 7= 5.3 Hz, 1H), 6.71 -6.63(m, 3H), 6.59 (d,7= 2.8 Hz, 1H), 5.65 (dq,7= 9.9, 6.1Hz, 1H), 4.61 - 4.46 (m, 1H), 4.39 (d, 7= 10.0 Hz, 1H), 3.94 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 2.37 (s, 3H),2.30(s, 3H), 1.30 (d, 7 = 6.2 Hz, 3H), 1.09 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 171.70, 168.56, 157.82, 157.67, 155.37, 148.74, 140.37, 137.93, 137.69, 131.88, 131.34, 130.50, 128.88, 128.13, 116.26, 116.08, 111.28, 110.86, 109.41, 75.02, 56.04, 55.08, 47.93, 46.22, 20.36, 20.30, 18.82, 17.78.
351
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
405 > (Thin film) 3368, 2937, 2837, 1732, 1650, 1609, 1578, 1529, 1504 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O9, 555.2337; found, 555.2327 3H NMR (300 MHz, CDC13) δ 12.16 (s, 1H), 8.37 (d, J= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.32 (d, J= 8.4 Hz, 1H), 7.11 (d, 7= 8.4 Hz, 1H), 6.85 (d, 7= 5.3 Hz, 1H), 6.42 - 6.34 (m, 3H), 6.32 (d, 7= 2.5 Hz, 1H), 5.88 (dq, 7= 9.8, 6.2 Hz, 1H), 4.82 (d, 7= 9.9 Hz, 1H), 4.61 -4.46(m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H).
406 A (Thin film) 3373, 2936, 1734, 1650, 1611, 1577, 1529, 1505 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2437 3H NMR (300 MHz, CDC13) δ 12.16 (d, 7= 0.6 Hz, 1H), 8.38 (d, 7= 8.0 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.30 (d, 7= 7.8 Hz, 1H), 7.10 (d, 7= 8.1Hz, 1H), 6.85 (dd,7 = 5.3, 0.6 Hz, 1H), 6.70-6.59 (m, 3H), 6.57-6.53 (m, 1H), 5.92 (dq, 7= 9.9, 6.2 Hz, 1H), 4.90 (d, 7= 9.9 Hz, 1H), 4.60 - 4.43 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.72 (s, 3H), 2.27 (s, 3H), 2.24 (s, 3H), 1.23 (d,7=6.2 Hz, 3H), 1.03 (d, 7= 7.2 Hz, 3H).
352
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
407 YS y A (Thin film) 3370, 2937, 2936, 1734, 1650, 1576, 1528, 1501 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2429 3H NMR (300 MHz, CDCh) δ 12.16 (d, J= 0.6 Hz, 1H), 8.38 (d, 7= 7.9 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.20 (d, 7= 2.2 Hz, 1H), 7.05 (d,7= 2.2 Hz, 1H), 6.98-6.84 (m, 2H), 6.85 (dd, 7= 5.4, 0.6 Hz, 1H), 6.74 (d, 7= 8.3 Hz, 1H), 6.64 (d, 7= 8.3 Hz, 1H), 5.88 (dq, 7= 10.2, 6.1 Hz, 1H), 4.96 (d, 7 = 10.3 Hz, 1H), 4.60 - 4.45 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.72 (s, 3H), 2.24 (s, 3H), 2.21 (s, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 1.02 (d,7= 7.2 Hz, 3H).
408 NS 'S* A (Thin film) 3368, 2940, 2839, 1736, 1650, 1577, 1528, 1478, 1453, 1434 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1942 3H NMR (300 MHz, CDCh) for both diastereomers of a 1:1 mixture d 12.14 (d, 7 = 0.7 Hz, 1H), 12.07 (d,7=0.6 Hz, 1H), 8.32 (d, 7= 8.6 Hz, 1H), 8.29 (d, 7= 8.4 Hz, 1H), 7.98 (d, 7= 5.3 Hz, 1H), 7.97 (d, 7= 5.2 Hz, 1H), 7.20-7.11 (m, 2H), 7.01 -6.82 (m, 12H), 5.825.63 (m,2H), 5.04 (d,7= 10.1 Hz, 1H), 5.03 (d,7=9.3 Hz, 1H), 4.63 - 4.42 (m, 2H), 3.96 (s, 3H), 3.95 (s, 3H), 3.93 (d, 7= 2.1 Hz, 3H), 3.90 (d, 7= 2.1 Hz, 3H), 3.78 (d, 7= 1.8 Hz, 3H), 3.78 (d, 7= 1.8 Hz, 3H), 1.37 (d, 7= 7.2 Hz, 3H), 1.27 (d, 7= 6.2 Hz, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 1.13 (d, 7= 7.2 Hz, 3H).
353
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
409 (Thin film) 3368, 2940, 2839, 1736, 1650, 1528, 1495, 1482 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1937 3H NMR (300 MHz, CDCh) for the major isomer of a 2:1 mixture of diastereomers d 12.09 (d, 7= 0.6 Hz, 1H), 8.37 (d, J= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.16 (dd, 7=9.6, 2.9 Hz, 1H), 6.96 (dd, 7= 9.3, 3.2 Hz, 1H), 6.90 - 6.75 (m, 4H), 6.72 (d, 7= 4.7 Hz, 1H), 5.98-5.79 (m, 1H), 4.91-4.83 (m, 1H), 4.62 - 4.46 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.73 (s, 3H), 1.25 (d,7=6.2 Hz, 3H), 1.11 (d, 7= 7.2 Hz, 3H).
354
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
410 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O9, 555.2337; found, 555.2317 'Η NMR (300 MHz, CDC13) for 1:1 mixture of diastereomers δ 12.20 (s, 1H), 12.11 (s, 1H), 8.37 (d, 7 = 7.8 Hz, 2H), 7.97 (t, 7 = 5.2 Hz, 2H), 7.09-6.81 (m, 10H), 6.78 - 6.68 (m, 4H), 5.79-5.59 (m, 2H), 5.11 (dd, 7= 9.8, 6.2 Hz, 2H), 4.52 (dp, 7= 10.0,7.1 Hz, 2H), 3.95 (s, 3H), 3.94 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.79 (s, 3H), 3.73 (s, 3H), 3.70 (s, 3H), 1.35 (d, 7= 7.2 Hz, 3H), 1.27 (d, 7= 4.7 Hz, 3H), 1.25 (d, 7= 4.7 Hz, 3H), 1.08 (d, 7= 7.2 Hz, 3H 13CNMR(126 MHz, CDCI3) for 1:1 mixture of diastereomers δ 171.68, 171.35, 168.48, 168.46, 155.31, 155.29, 152.81, 152.79, 152.74, 152.72, 148.71, 148.67, 147.33, 147.31, 147.15, 147.12, 140.36, 134.98, 134.79, 134.67, 134.47, 130.57, 130.50, 123.69, 123.65, 123.62, 121.03, 120.94, 120.41, 120.24, 110.79, 110.57, 110.55, 109.35, 109.33, 73.98, 60.39, 60.37, 60.27, 56.07, 56.05, 55.65, 55.57, 55.55,47.92, 47.90, 41.96,41.92, 18.80, 18.72, 18.04, 17.74.
355
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Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
411 SO HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2409 'Η NMR (300 MHz, CDCh) for 1:1 mixture of diastereomers δ 12.20 (d, J = 0.5 Hz, 1H), 12.11 (d,7=0.5 Hz, 1H), 8.36 (d, J= 7.8 Hz, 2H), 7.98 (dd, J= 5.9, 5.2 Hz, 2H), 7.32 (ddd, J= 12.0, 7.2, 2.1 Hz, 2H), 7.17-7.09 (m, 2H), 7.09-6.80 (m, 10H), 5.76 - 5.57 (m,2H), 5.08 (t, 7= 9.6 Hz, 2H), 4.59 -4.41 (m,2H), 3.96 (s, 3H), 3.94 (s, 3H), 3.83 (s, 3H), 3.79 (s, 3H), 3.69 (s, 3H), 3.68 (s, 3H), 2.36-2.19 (m, 12H), 1.33 - 1.23 (m, 9H), 1.02 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) for 1:1 mixture of diastereomers δ 171.66, 171.15, 168.48, 168.46, 156.89, 156.80, 156.76, 155.32, 148.74, 148.69, 140.38, 140.33, 133.98, 133.84, 133.74, 133.69, 131.21, 131.19, 131.02, 130.98, 130.56, 130.47, 130.09, 130.04, 129.77, 129.74, 126.86, 126.71, 126.59, 126.34, 123.84, 123.80, 123.73, 109.36, 74.58, 74.50, 60.29, 60.22, 60.19, 56.08, 56.07, 47.89, 47.85,41.76,41.70, 19.02, 18.93, 18.03, 17.65, 16.69, 16.66, 16.48, 16.45.
356
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
412 as X 1H NMR (400 MHz, CDCh) for 1:1 mixture of diastereomers δ 12.18 (s, 1H), 12.11 (s, 1H), 8.36 (d, 7 = 7.9 Hz, 1H), 8.28 (d,7= 7.7 Hz, 1H), 8.06-7.91 (m, 2H), 7.11-7.00 (m, 4H), 6.95 (t, 7= 8.6 Hz, 2H), 6.89 -6.82 (m, 4H), 6.70 (d,7= 8.2 Hz, 2H), 6.65 (dd,7= 8.0, 4.5 Hz, 2H), 5.70 (ddq,7 = 12.3, 6.1, 3.3, 2.6 Hz, 2H), 4.62 (dd,7= 12.2, 9.9 Hz, 2H), 4.49 (dp, 7= 22.0, 7.2 Hz, 2H), 3.94 (s, 3H), 3.93 (s, 3H), 3.79 (s, 3H), 3.79 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 2.29 (s, 3H), 2.26 (s, 3H), 2.19 (s, 3H), 2.18 (s, 3H), 1.35- 1.25 (m, 9H), 1.05 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) for 1:1 mixture of diastereomers δ 171.69, 171.27, 168.52, 157.74, 157.55, 155.32, 148.73, 140.69, 140.38, 140.12, 139.96, 130.52, 126.17, 126.11, 125.90, 125.55, 125.38, 120.47, 120.38, 119.87, 119.66, 109.38, 108.32, 74.97, 74.87, 56.03, 55.46, 55.43, 47.92, 47.89, 47.53, 18.74, 18.72, 17.98, 17.69, 11.84, 11.74, 11.42.
357
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
413 A (Thin film) 3374, 2941, 1737, 1650, 1529, 1501, 1476, 1453, 1431, 1281, 1263, 1243, 1058, 952, 801 HRMS-ESI (m/z) ([M+H]+) calcd for C27H27F4N2O7, 567.1749; found, 567.1750 1H NMR (400 MHz, CDCI3) 612.03 (s, 1H), 8.28 (d,7= 8.0 Hz, 1H), 7.96 (d,7=5.3 Hz, 1H), 7.05 (ddd, J= 8.4, 5.6, 2.2 Hz, 1H), 6.89-6.72 (m, 4H), 5.67 (dq,7=9.6, 6.2 Hz, 1H), 4.86 (d,7=9.6 Hz, 1H), 4.56 (dt, 7=8.1, 7.0 Hz, 1H), 3.97 (d,7=2.4 Hz, 3H), 3.95 (s, 3H), 3.83 (d, 7= 2.1 Hz, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.20 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCb) δ 171.48, 168.61, 155.43, 148.73, 147.12 (d, 7 = 7.3 Hz), 146.96 (d,7=7.6 Hz), 145.26 (d, 7= 13.9 Hz), 143.28 (d, 7= 13.8 Hz), 140.44, 130.25, 129.70, 129.47, 123.09 (dd, 7= 8.2, 3.8 Hz), 122.45- 122.20 (m), 110.82 (d, 7 = 17.3 Hz), 110.57, 109.47, 72.53, 61.22 (d, 7=4.1 Hz), 61.16 (d, 7= 3.6 Hz), 56.11, 47.96, 42.46, 18.74, 17.75.
358
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
414 y & (Thin film) 3369, 2925, 1735, 1650, 1576, 1528, 1501, 1481, 1451, 1331, 1280, 1263, 1212, 1145, 1045, 801, 733 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O5, 491.2540; found, 491.2536 3H NMR (400 MHz, CDCfi) δ 12.11 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.11 -7.00 (m, 3H), 6.94-6.84 (m, 4H), 5.73-5.64 (m, 1H), 4.554.44 (m, 2H), 3.94 (s, 3H), 2.36 (s, 3H), 2.28 (s, 3H), 2.26 (s, 6H), 1.30 (d, 7= 6.1 Hz, 3H), 1.03 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 171.84, 168.52, 155.34, 148.73, 140.40, 139.09, 138.45, 135.47, 135.11, 133.53, 133.33, 130.60, 130.49, 130.27, 128.60, 127.81, 127.27, 126.95, 109.39, 75.10, 56.07, 47.89, 47.34, 21.29, 21.22, 19.79, 19.75, 18.78, 17.66.
359
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
415 ON X (Thin film) 3369, 2937, 1734, 1649, 1576, 1527, 1500, 1480, 1450, 1329, 1280, 1262, 1242, 1139, 1043, 908, 799, 728 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O5, 491.2540; found, 491.2536 1H NMR (400 MHz, CDCh) δ 12.11 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.18 (d, J= 7.9 Hz, 1H), 7.12 (d, J= 7.7 Hz, 1H), 6.98 - 6.89 (m, 3H), 6.87-6.81 (m, 2H), 5.69 (dq, 7= 10.0, 6.2 Hz, 1H), 4.58-4.48 (m, 1H), 4.45 (d, 7= 10.0 Hz, 1H), 3.94 (s, 3H), 2.35 (s, 3H), 2.29 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.30 (d, 7= 6.2 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.71, 168.51, 155.32, 148.69, 140.38, 136.43, 136.33, 136.15, 135.95, 135.90, 135.58, 131.50, 131.15, 130.49, 127.77, 127.05, 126.85, 126.58, 109.37, 75.04, 56.06, 47.89, 46.81, 20.84, 20.80, 20.12, 20.07, 18.85, 17.71.
360
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
416 δ (Thin film) 3369, 2938, 1736, 1649, 1576, 1528, 1494, 1480, 1452, 1326, 1279, 1263, 1240, 1184, 1145, 1044, 910, 803, 728 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O5, 499.2039; found, 499.2035 1H NMR (400 MHz, CDCh) 612.05 (s, 1H), 8.36 (d, J= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.12 (dd, J= 8.4, 6.0 Hz, 1H), 7.06 - 7.00 (m, 2H), 6.93 - 6.77 (m, 4H), 5.60 (dq, 7=9.6, 6.2 Hz, 1H), 4.61-4.50 (m, 1H), 4.48 (d, J= 9.6 Hz, 1H), 3.94 (s, 3H), 2.35 (s, 3H), 2.28 (s, 3H), 1.34 (d, 7= 6.2 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.60, 168.60, 161.36 (d, 7= 244.0 Hz), 155.35, 148.72, 140.57 (d, 7 = 6.5 Hz), 140.48, 139.99 (d, 7= 6.6 Hz), 132.34 (d,7 = 3.2 Hz), 132.07 (d,7=7.8 Hz), 132.00 (d, 7= 3.3 Hz), 131.72 (d, 7= 7.9 Hz), 130.39, 114.85 (d, 7= 22.3 Hz), 114.32 (d, 7= 22.3 Hz), 113.72 (d, 7= 20.7 Hz), 113.42 (d, 7= 20.5 Hz), 109.44, 74.21, 56.08, 47.79, 47.70, 19.41, 19.36, 18.76, 17.68.
361
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
417 ss (Thin film) 3367, 2940, 1738, 1650, 1530, 1498, 1482, 1453, 1281, 1264, 1242, 1210, 1149, 1037, 802, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1931 3H NMR (400 MHz, CDC13) δ 12.07 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.01 -6.90 (m, 2H), 6.88 - 6.80 (m, 3H), 6.71 (ddd, J= 8.9, 3.9, 3.1 Hz, 1H), 6.64 (ddd, J= 8.9, 3.9, 3.1Hz, 1H), 5.85 (dq,7 = 12.2, 6.1 Hz, 1H), 4.70 (d, J= 10.4 Hz, 1H), 4.61-4.52 (m, 1H), 3.94 (s, 3H), 3.74 (s, 6H), 1.31 (d, J= 6.1 Hz, 3H), 1.11 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.53, 168.53, 155.99 (d, 7= 24.2 Hz), 155.76- 155.59 (m), 155.32, 154.09 (d, 7= 24.6 Hz), 148.70, 140.40, 130.42, 127.85 (d, 7= 15.9 Hz), 127.56 (d, 7= 16.3 Hz), 116.26 (d, 7= 24.9 Hz), 115.93 (d, 7= 24.8 Hz), 115.16, 114.19, 113.04 (d, J = 8.2 Hz), 109.39, 72.25, 56.07, 55.69, 47.85, 43.42, 18.94, 17.72.
362
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
418 (Thin film) 3369, 2938, 1737, 1650, 1623, 1577, 1529, 1507, 1481, 1443, 1320, 1282, 1264, 1242, 1195, 1154, 1031, 951, 849, 834, 800, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1933 1H NMR (400 MHz, CDCfi) δ 12.09 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.27 (t, 7= 8.6 Hz, 1H), 7.16 (t, 7= 8.5 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.64 -6.54(m, 3H), 6.47 (dd,7= 12.1, 2.6 Hz, 1H), 5.79 (dq,7 = 12.0, 6.1 Hz, 1H), 4.664.52 (m, 2H), 3.94 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 1.28 (d,7=6.1 Hz, 3H), 1.14 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 171.55, 168.55, 161.19 (d, 7= 245.6 Hz), 161.00 (d, 7= 245.8 Hz), 159.75 (d,7= 11.3 Hz), 159.47 (d,7= 11.3 Hz), 155.35, 148.69, 140.39, 130.42, 129.87 (d, 7= 6.2 Hz), 129.23 (d, 7= 5.9 Hz), 119.53 (d,7= 14.6 Hz), 119.33 (d,7= 15.0 Hz), 110.16 (d, 7= 3.0 Hz), 109.66 (d, 7= 3.0 Hz), 109.38, 101.82 (d, 7= 26.7 Hz), 101.59 (d, 7= 26.6 Hz), 72.49, 56.05, 55.48 (d, 7= 6.8 Hz), 47.90, 41.70, 18.91, 17.79.
363
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
419 A A (Thin film) 3370, 2941, 1737, 1651, 1616, 1577, 1529, 1454, 1417, 1326, 1241, 1119, 1080, 1032, 905, 860, 801, 738 HRMS-ESI (m/z) ([M+H]+) calcd for C29H29F6N2O7, 631.1873; found, 631.1876 3H NMR (400 MHz, CDCf) δ 12.06 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.54 (d, 7= 7.8 Hz, 1H), 7.30 (d, 7= 8.0 Hz, 1H), 7.12 (dd, 7= 7.9, 1.6 Hz, 2H), 7.04 (d, 7 = 1.8 Hz, 1H), 6.98 (d, 7= 1.7 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 5.99 (dq, 7= 9.5, 6.2 Hz, 1H), 5.00 (d, 7= 9.4 Hz, 1H), 4.59-4.48 (m, 1H), 3.94 (s, 3H), 3.89 (s, 3H), 3.81 (s, 3H), 1.26 (d,7=6.2 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCf) δ 171.62, 168.58, 157.53, 155.38, 148.73, 140.44, 132.32 (d, 7= 8.6 Hz), 130.37, 130.18, 130.04, 129.47, 125.02, 122.83, 117.30, 116.98, 109.43, 107.83- 106.97 (m), 72.18, 56.07, 55.75, 55.69, 47.82, 18.89, 17.66.
364
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
420 sc cn (Thin film) 3369, 2940, 1737, 1592, 1453, 1135, 1057, 849, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1924 3H NMR (500 MHz, CDCh) δ 12.04 (d, 7= 0.6 Hz, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.65-6.52 (m, 4H), 6.45 (ddt, 7= 24.3, 10.5,2.2 Hz, 2H), 5.69 (dq,7 = 10.1, 6.1 Hz, 1H), 4.61 4.50 (m, 1H), 3.97-3.91 (m, 4H), 3.77 (s, 3H), 3.75 (s, 3H), 1.29- 1.24 (m, 3H), 1.11 (d, 7= 7.2 Hz, 3H).
19F NMR (471 MHz, CDCh) 6-110.48--110.65 (m), 111.08 (t, 7= 10.0 Hz).
421 sc CN (Thin film) 3371,2938, 1735, 1593, 1454, 1204, 1150, 1063, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O9, 555.2337; found, 555.2329 3H NMR (500 MHz, CDCh) δ 12.10 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.46 - 6.43 (m, 4H), 6.27 (dt, 7=26.6, 2.2 Hz, 2H), 5.75 (dq, 7= 10.3,6.1 Hz, 1H), 4.58-4.47 (m, 1H), 3.94 (s, 3H), 3.89 (d,7 = 10.5 Hz, 1H), 3.76 (s, 6H), 3.74 (s, 6H), 1.30- 1.23 (m, 3H), 1.05 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.70, 168.53, 160.93, 160.75, 155.32, 148.71, 143.38, 143.10, 140.39, 130.45, 109.36, 106.42, 106.08, 98.42, 98.35, 73.11, 58.22, 56.06, 55.30, 55.26, 47.87, 19.21, 17.70.
365
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
422 M a (Thin film) 3372, 2937, 1735, 1594, 1528, 1452, 1151, 1065, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2434 1H NMR (500 MHz, CDC13) δ 12.11 (s, 1H), 8.36 (d, J= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.69 (dd,7=3.8,1.8 Hz, 2H), 6.64 (t, 7= 1.9 Hz, 2H), 6.55 (t, 7= 2.0 Hz, 1H), 6.49 (t, 7= 1.9 Hz, 1H), 5.75 (dq,7=10.5, 6.2 Hz, 1H), 4.58-4.48 (m, 1H), 3.94 (s, 3H), 3.89 (d,7= 10.5 Hz, 1H), 3.76 (s, 3H), 3.73 (s, 3H), 2.29 (s, 3H), 2.25 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.1 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.74, 168.51, 159.74, 159.61, 155.32, 148.70, 142.68, 142.37, 140.40, 139.79, 139.36, 130.47, 121.27, 121.12, 112.62, 112.61, 111.34, 110.82, 109.36, 73.43, 57.89, 56.06, 55.15, 55.11,47.86, 21.69,21.61, 19.25, 17.66.
366
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
423 AN M (Thin film) 3370, 2937, 1734, 1649, 1528, 1452, 1260, 1137, 1039, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2434 1H NMR (500 MHz, CDCR) δ 12.10 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.02 (dd, 7=7.5, 0.9 Hz, 1H), 6.97 (dd,7 = 7.6, 0.8 Hz, 1H), 6.86 (d,7 = 5.2 Hz, 1H), 6.80 (dt,7= 7.5, 2.1 Hz, 2H), 6.74 (d,7 = 1.6 Hz, 1H), 6.71 (d,7= 1.6 Hz, 1H), 5.80 (dq, 7 = 10.3, 6.1Hz, 1H), 4.58-4.47 (m, 1H), 3.96 (d, 7= 10.3 Hz, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 3.78 (s, 3H), 2.14 (s, 3H), 2.11 (s, 3H), 1.27 (d,7 = 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H).
424 X (Thin film) 3370, 2938, 1736, 1515, 1442, 1275, 1216, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O7, 531.1937; found, 531.1935 1H NMR (500 MHz, CDCR) 612.05 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.01-6.91 (m, 4H), 6.91 - 6.79 (m, 3H), 5.65 (dq, 7=9.6, 6.2 Hz, 1H), 4.61-4.51 (m, 1H), 3.94 (s, 3H), 3.92 (d,7=9.7 Hz, 1H), 3.85 (s, 3H), 3.83 (s, 3H), 1.24 (d, 7= 6.1 Hz, 3H), 1.13 (d, 7= 7.2 Hz, 3H). 19F NMR (471 MHz, CDCR) δ-134.12 (dd, 7= 12.1,8.5 Hz),-134.58 (dd, 7= 12.1, 8.7 Hz).
367
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
425 AG ss ¥ (Thin film) 3370, 2941, 1734, 1649, 1503, 1243, 1135, 1033, 801, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2428 1H NMR (500 MHz, CDCh) δ 12.13 (d,/= 0.6 Hz, 1H), 8.36 (d,/= 8.1 Hz, 1H), 7.98 (d,/=5.1Hz, 1H), 7.06 (ddd,/=9.0, 7.1,2.4 Hz, 2H), 7.01 (d,/= 2.0 Hz, 2H), 6.86 (d,/= 5.2 Hz, 1H), 6.72 (d,/= 8.4 Hz, 1H), 6.68 (d,/= 8.4 Hz, 1H), 5.71 (dq,/= 10.1,6.1 Hz, 1H), 4.58-4.48 (m, 1H), 3.94 (s, 3H), 3.88 (d,/ = 10.1 Hz, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H), 1.24 (d,/= 6.2 Hz, 3H), 1.03 (d,/= 7.1 Hz, 3H).
368
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
426 A A (Thin film) 3372, 2940, 1735, 1650, 1498, 1223, 1047, 804, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O9, 555.2337; found, 555.2304 1H NMR (500 MHz, CDCh) δ 12.14 (s, 1H), 8.38 (d, J= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.05 (d, 7= 3.0 Hz, 1H), 6.88 (d, 7= 3.1 Hz, 1H), 6.85 (d, 7= 5.2 Hz, 1H), 6.77 (d, 7= 8.9 Hz, 1H), 6.72-6.55 (m, 3H), 5.94 (dq, 7= 10.1,6.1 Hz, 1H), 4.93 (d, 7= 10.1 Hz, 1H), 4.60 - 4.49 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 3.71 (s, 6H), 1.28- 1.22 (m, 3H), 1.04 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.72, 168.47, 155.28, 153.41, 153.37, 151.78, 151.70, 148.67, 140.35, 130.55, 130.51, 116.43, 115.36, 112.05, 112.00, 111.68, 111.46, 109.31, 73.26, 56.27, 56.05, 55.62, 55.57, 47.90, 18.87, 17.81.
369
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
427 AS os (Thin film) 3370, 2939, 1736, 1529, 1452, 1243, 1143, 1043, 801, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C29H35N2O7, 523.2439; found, 523.2420 3H NMR (500 MHz, CDCfi) δ 12.10 (s, 1H), 8.36 (d, J= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.06 (d, 7= 8.4 Hz, 1H), 6.95 (d, 7= 8.4 Hz, 1H), 6.90 (d, 7= 2.7 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.82 (d, 7= 2.7 Hz, 1H), 6.66 (dd, 7= 8.4, 2.7 Hz, 1H), 6.60 (dd, 7=8.3, 2.7 Hz, 1H), 5.67 (dq,7 = 10.0, 6.2 Hz, 1H), 4.584.49 (m, 1H), 4.46 (d,7= 10.1 Hz, 1H), 3.94 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.34 (s, 3H), 2.26 (s, 3H), 1.32 (d, 7= 6.2 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H).
428 (Thin film) 3368, 2933, 1736, 1648, 1528, 1492, 1481, 1263, 1094 HRMS-ESI (m/z) ([M+H]+) calcd for C29H33F2N2O7, 560.2283; found, 560.2285 3H NMR (400 MHz, CDCfi) 612.05 (s, 1H), 8.32 (d,7= 7.9 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.43 (dd, 7=8.7, 5.6 Hz, 1H), 7.23 (dd,7 = 8.7, 5.6 Hz, 1H), 7.11 (dd,7 = 9.6, 2.8 Hz, 1H), 7.04 (dd, 7=9.6, 2.8 Hz, 1H), 6.966.89 (m,2H), 6.87 (d,7=5.2 Hz, 1H), 5.63 (dq, 7=8.7, 6.2 Hz, 1H), 4.71 (d,7=8.8 Hz, 1H), 4.63 (d, 7 = 12.4 Hz, 1H), 4.58-4.36 (m, 4H), 3.94 (s, 3H), 3.43 (s, 3H),3.38(s, 3H), 1.30 (d, 7 = 6.2 Hz, 3H), 1.12 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ-115.46, -115.76.
370
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
429 Ύ ss (Thin film) 3369, 2975, 1736, 1649, 1527, 1481, 1262, 1093 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37F2N2O7, 587.2563; found, 587.2559 1H NMR (400 MHz, CDCh) δ 12.06 (s, 1H), 8.33 (d,7= 7.9 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.45 (dd,7=8.7, 5.6 Hz, 1H), 7.21 (dd,7 = 8.7, 5.6 Hz, 1H), 7.12 (dd, 7 = 9.6, 2.8 Hz, 1H), 7.07 (dd, 7=9.7, 2.8 Hz, 1H), 6.946.84 (m, 3H), 5.73 - 5.56 (m, 1H), 4.78 - 4.63 (m, 2H), 4.60-4.38 (m, 4H), 3.94 (s, 3H), 3.62-3.42 (m, 4H), 1.33 - 1.25 (m, 6H), 1.23 (t, 7= 7.0 Hz, 3H), 1.12 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ -115.57, -115.85.
430 's· Y HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O6, 483.1931; found, 483.1928 1H NMR (400 MHz, CDCh) δ 12.11 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.3 Hz, 1H), 7.48 - 7.07 (m, 6H), 6.85 (d, 7= 5.3 Hz, 1H), 6.58 (t, 7=8.3 Hz, 2H), 5.85 (dd, 7= 10.1, 6.0 Hz, 1H), 4.724.38 (m, 2H), 3.93 (s, 3H), 3.83 (s, 3H), 1.25 (d,7=6.2 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.13.
371
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
431 A k A HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1982; found, 467.1976 1H NMR (400 MHz, CDCI3) δ 12.09 (s, 1H), 8.33 (d,7= 7.9 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.36 - 7.07 (m, 6H), 6.94 - 6.78 (m, 3H), 5.78 (dq, 7= 10.4, 6.1 Hz, 1H), 4.52 (p, 7= 7.3 Hz, 1H), 4.29 (d, 7= 10.3 Hz, 1H), 3.93 (s, 3H),2.39(s, 3H), 1.28 (d,7 = 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCI3) δ-116.60.
432 HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O6, 483.1931; found, 483.1931 1H NMR (400 MHz, CDCI3) δ 12.09 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.47 - 7.20 (m, 5H), 7.20-7.10 (m, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 6.57 (td, 7= 8.3, 2.6 Hz, 1H), 6.49 (dd, 7 = 10.9, 2.5 Hz, 1H), 5.83 (dq,7= 10.2, 6.1Hz, 1H), 4.61 -4.49 (m,2H), 3.94 (s, 3H), 3.76 (s, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 1.07 (d,7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCI3) δ-113.49.
372
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
433 o <R« A HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1982; found, 467.1974 1H NMR (400 MHz, CDCfi) δ 12.07 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.35 (dd, J= 8.7, 5.7 Hz, 1H), 7.31-7.13 (m, 5H), 6.92 - 6.80 (m, 2H), 6.76 (dd,7=9.7, 2.8 Hz, 1H), 5.75 (dq, J= 10.1,6.1 Hz, 1H), 4.53 (p, 7= 7.3 Hz, 1H), 4.26 (d, 7= 10.1 Hz, 1H), 3.93 (s, 3H), 2.30 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ-116.99.
434 QR NQ QS A A HRMS-ESI (m/z) ([M+H]+) calcd for C27H30FN2O6, 497.2088; found, 497.2077 1H NMR (400 MHz, CDCfi) δ 12.12 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.19 (d, 7= 8.0 Hz, 2H), 7.17-7.08 (m, 1H), 7.01 (d, 7= 8.0 Hz, 2H), 6.86 (d, 7= 5.2 Hz, 1H), 6.646.51 (m, 2H), 5.82 (dq,7 = 9.9, 6.2 Hz, 1H), 4.63 -4.41 (m, 2H), 3.94 (s, 3H), 3.83 (s, 3H), 2.25 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.03 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ -113.38.
373
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
435 A γ 'j HRMS-ESI (m/z) ([M+H]+) calcd for C27H30FN2O5, 481.2139; found, 481.2133 XH NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.38-7.26 (m, 1H), 7.13 (d, 7= 8.1 Hz, 2H), 7.00 (d, 7= 8.0 Hz, 2H), 6.956.80 (m, 3H), 5.76 (dq,7 = 10.2, 6.2 Hz, 1H), 4.53 (p,7 = 7.3 Hz, 1H), 4.25 (d,7= 10.2 Hz, 1H), 3.93 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H), 1.27 (d, 7= 6.1 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-116.80.
436 A A A HRMS-ESI (m/z) ([M+H]+) calcd for C27H30FN2O6, 497.2088; found, 497.2076 1H NMR (400 MHz, CDCh) δ 12.10 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.33 - 7.22 (m, 1H), 7.19-7.13 (m,2H), 7.06 (d, 7= 7.8 Hz, 2H), 6.85 (d,7= 5.2 Hz, 1H), 6.56 (td, 7= 8.3, 2.6 Hz, 1H), 6.48 (dd, 7 = 10.9, 2.5 Hz, 1H), 5.80 (dq,7= 10.4, 6.1Hz, 1H), 4.62-4.44 (m, 2H), 3.94 (s, 3H), 3.76 (s, 3H), 2.28 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 1.06 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.69.
374
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
437 V A V HRMS-ESI (m/z) ([M+H]+) calcd for C27H30FN2O5, 481.2139; found, 481.2121 3H NMR (400 MHz, CDC13) δ 12.07 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.33 (dd, J= 8.7, 5.8 Hz, 1H), 7.18-7.00 (m, 4H), 6.94 - 6.81 (m, 2H), 6.74 (dd, 7=9.7, 2.8 Hz, 1H), 5.73 (dq, 7= 10.1, 6.1 Hz, 1H), 4.52 (p, J= 7.3 Hz, 1H), 4.22 (d, 7= 10.3 Hz, 1H), 3.94 (s, 3H), 2.29 (s, 3H), 2.28 (s, 3H), 1.25 (d,7 = 6.1 Hz, 3H), 1.04 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-117.22.
438 V HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O6, 501.1837; found, 501.1829 1H NMR (400 MHz, CDCI3) δ 12.09 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.31-7.23 (m,2H), 7.12 (dd, J= 8.2, 6.5 Hz, 1H), 6.94 - 6.80 (m, 3H), 6.64 - 6.52 (m, 2H), 5.81 (dq, 7= 10.0, 6.2 Hz, 1H), 4.61 -4.38 (m,2H), 3.94 (s, 3H), 3.83 (s, 3H), 1.25 (d,7 = 6.2 Hz, 3H), 1.06 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDC13) δ-112.82, -116.36.
375
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
439 HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O5, 485.1888; found, 485.1874 1H NMR (400 MHz, CDCh) δ 12.08 (s, 1H), 8.33 (d,7= 7.9 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.33 -7.12 (m, 3H), 6.97 - 6.83 (m, 5H), 5.73 (dq, J= 9.9, 6.1Hz, 1H), 4.68 - 4.46 (m, 1H), 4.28 (d, J= 10.1 Hz, 1H), 3.94 (s, 3H), 2.36 (s, 3H), 1.28 (d,7 = 6.1 Hz, 3H), 1.09 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-115.88, -116.28.
440 'S’ HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O6, 501.1837; found, 501.1824 1H NMR (400 MHz, CDCh) δ 12.08 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.30-7.19 (m, 3H), 6.99 - 6.90 (m, 2H), 6.86 (d, J= 5.3 Hz, 1H), 6.57 (td, J= 8.3, 2.5 Hz, 1H), 6.50 (dd,7 = 10.9, 2.5 Hz, 1H), 5.925.68 (m, 1H), 4.64 - 4.40 (m, 2H), 3.94 (s, 3H), 3.76 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.15, -116.03.
376
2019201931 20 Mar 2019
Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
441 Ύ HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O5, 485.1888; found, 485.1876 1H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.96 (d,7=5.2 Hz, 1H), 7.33 (dd, J= 8.7, 5.7 Hz, 1H), 7.19 (dd, J= 8.5, 5.4 Hz, 2H), 7.02-6.90 (m, 2H), 6.91 - 6.82 (m, 2H), 6.77 (dd, 7=9.7, 2.8 Hz, 1H), 5.71 (dq, J= 9.8, 6.1 Hz, 1H), 4.53 (p, 7= 7.3 Hz, 1H), 4.26 (d, 7= 9.9 Hz, 1H), 3.93 (s, 3H), 2.27 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-115.42, -116.65.
442 V· A X (Thin film) 3376, 2929, 1736, 1650, 1576, 1529, 1481, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C27H31N2O5, 463.2224; found, 463.2227 1H NMR (400 MHz, CDCI3) δ 12.11 (s, 1H), 8.35 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.20-7.13 (m, 1H), 7.12-7.06 (m, 5H), 7.03 - 6.97 (m, 1H), 6.96 6.92 (m, 1H), 6.85 (d,7=5.2 Hz, 1H), 5.79 (dq, 7 = 10.3, 6.1Hz, 1H), 4.57-4.44 (m, 1H), 3.97 (d, 7= 10.4 Hz, 1H), 3.93 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.25 (d,7 = 6.1 Hz, 3H), 0.97 (d,7= 7.2 Hz, 3H).
377
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (Y, 13c, 19f)
443 'S NS SN HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O6, 516.2021; found, 516.2018 3H NMR (400 MHz, CDC13) δ 12.09 (s, 1H), 8.35 (d, J= 7.7 Hz, 1H), 7.97 (d,/= 5.2 Hz, 1H), 7.23 (dd,/=8.5, 6.6 Hz, 1H), 7.17 (dd, J= 8.6, 5.8 Hz, 1H), 6.90-6.73 (m,2H), 6.57 (td, J= 8.3, 2.5 Hz, 1H), 6.49 (dd, J= 10.8, 2.5 Hz, 1H), 5.70 (dq,/= 10.1, 6.1 Hz, 2H), 4.75 (d,/ = 10.2 Hz, 1H), 4.55 (p,/= 7.3 Hz, 1H), 3.94 (s, 3H), 3.76 (s, 3H), 2.43 (s, 3H), 1.24 (d,/= 6.2 Hz, 3H), 1.12 (d, /= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCI3) δ-113.36, -116.89.
444 '•S Y SN HRMS-ESI (m/z) ([M+H]+) calcd for C26H26F3N2O6, 519.1737; found, 519.1734 3H NMR (400 MHz, CDCI3) δ 12.07 (s, 1H), 8.33 (d,/= 7.9 Hz, 1H), 7.97 (d,/= 5.2 Hz, 1H), 7.29 (dd,/=8.4, 6.7 Hz, 1H), 7.25-7.14 (m, 1H), 6.86 (d,/= 5.2 Hz, 1H), 6.81-6.70 (m, 2H), 6.56 (td,/= 8.3, 2.5 Hz, 1H), 6.50 (dd,/= 10.8, 2.5 Hz, 1H), 5.82 (dq,/= 11.5, 6.2 Hz, 1H), 4.78 (d,/= 10.1 Hz, 1H), 4.55 (p,/= 7.2 Hz, 1H), 3.94 (s, 3H), 3.75 (s, 3H), 1.26 (d,/= 6.1 Hz, 3H), 1.12 (d,/= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCI3) δ-112.12 (d, J = 7.5 Hz), 112.18 (d, J = 7.5 Hz), 112.75
378
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
445 >V\ \y X > HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O6, 516.2021; found, 516.2021 1H NMR (400 MHz, CDCh) δ 12.08 (s, 1H), 8.33 (d,7= 7.9 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.32 (dd, J= 8.6, 5.8 Hz, 1H), 7.03 (dd,7 = 8.3, 6.7 Hz, 1H), 6.86 (d,7 = 5.2 Hz, 1H), 6.81 (td,7= 8.5, 2.8 Hz, 1H), 6.75 (dd,7 = 9.7, 2.7 Hz, 1H), 6.62 6.51 (m, 2H), 5.69 (dq,7 = 10.0, 6.2 Hz, 1H), 4.76 (d,7 = 9.8 Hz, 1H), 4.53 (p,7= 7.2 Hz, 1H), 3.94 (s, 3H), 3.84 (s, 3H), 2.26 (s, 3H), 1.27 (d, J= 6.2 Hz, 3H), 1.07 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-112.84, -117.29.
446 X NS HRMS-ESI (m/z) ([M+H]+) calcd for C26H26F3N2O5, 504.1821; found, 504.1818 1H NMR (400 MHz, CDCh) δ 12.04 (s, 1H), 8.31 (d,7= 7.8 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.32 (dd, 7= 8.6, 5.7 Hz, 1H), 7.18-7.07 (m, 1H), 6.90 - 6.72 (m, 5H), 5.70 (dq, 7= 11.7,6.4 Hz, 1H), 4.64 (d, 7= 10.0 Hz, 1H), 4.54 (p, 7= 7.2 Hz, 1H), 3.94 (s, 3H), 2.27 (s, 3H), 1.29 (d, 7= 6.1 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-111.40 (d,7=7.6Hz),112.58 (d, 7= 7.6 Hz),116.32.
379
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
447 sc sn SN (Thin film) 3373, 2980, 2938, 1737, 1650, 1576, 1530, 1481, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1977; found, 467.1974 3H NMR (400 MHz, CDCf) δ 12.30- 12.00 (m, 1H), 8.36 (d, J= 8.0 Hz, 1H), 7.96 (dd, 7=5.2, 1.5 Hz, 1H), 7.39-7.12 (m, 6H), 6.896.82 (m, 2H), 6.72 (dd,7 = 11.3, 1.6 Hz, 1H), 5.82 (dq,7 = 9.8, 6.0 Hz, 1H), 4.56 (p, 7 = 7.3 Hz, 1H), 4.41 (d,7= 10.1 Hz, 1H), 3.92 (s, 3H), 2.23 (s, 3H), 1.26 (d,7=6.1 Hz, 3H), 1.09 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCf) δ-118.95.
448 SC SN sn SN (Thin film) 3377, 2983, 1737, 1650, 1577, 1530, 1510, 1481, 1453, 1440 HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O5, 485.1883; found, 485.1877 1H NMR (400 MHz, CDCf) δ 12.07 (d, 7= 0.6 Hz, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.297.23 (m, 2H), 7.21 (t, 7= 7.9 Hz, 1H), 7.00 - 6.93 (m, 2H), 6.89-6.84 (m, 2H), 6.75-6.71 (m, 1H), 5.81 5.68 (m, 1H), 4.60-4.49 (m, 1H), 4.39 (d, 7= 10.1 Hz, 1H), 3.94 (s, 3H), 2.24 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.10 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCf) δ-115.56, -118.95.
380
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
449 NS Y (Thin film) 3378, 2982, 2932, 1738, 1650, 1576, 1530, 1481, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C27H30FN2O5, 481.2133; found, 481.2133 3H NMR (400 MHz, CDC13) δ 12.10 (s, 1H), 8.36 (d, J= 8.0 Hz, 1H), 7.97 (d,7=5.1 Hz, 1H), 7.28-7.12 (m, 3H), 7.08 (d, 7= 7.8 Hz, 2H), 6.88-6.81 (m, 2H), 6.71 (d, 7= 11.2 Hz, 1H), 5.80 (dq, 7= 12.1,6.2 Hz, 1H), 4.55 (p, 7= 7.3 Hz, 1H), 4.38 (d, 7= 10.1 Hz, 1H), 3.92 (s, 3H), 2.28 (s, 3H), 2.22 (s, 3H), 1.26 (d,7 = 6.1 Hz, 3H), 1.09 (d,7= 7.0 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-119.09.
450 γ NS (Thin film) 3373, 2982, 1737, 1651, 1577, 1530, 1482, 1453 HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O5, 499.2039; found, 499.2033 3H NMR (400 MHz, CDCI3) δ 12.09 (d, 7= 0.6 Hz, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.24 (dd, 7=9.4, 5.5 Hz, 1H), 7.15 (t, 7= 7.9 Hz, 1H), 6.90-6.78 (m, 4H), 6.75 - 6.67 (m, 1H), 5.79-5.68 (m, 1H), 4.64 (d, 7= 10.2 Hz, 1H), 4.61 -4.52 (m, 1H), 3.94 (s, 3H), 2.39 (s, 3H), 2.24 (s, 3H), 1.27 (d, 7= 6.2 Hz, 3H), 1.13 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-116.44, -118.17.
381
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
451 iY (Thin film) 3375, 2982, 2939, 1739, 1651, 1577, 1530, 1504, 1481, 1453 HRMS-ESI (m/z) ([M+H]+) calcd for C26H26F3N2O5, 503.1788; found, 503.1784 1H NMR (400 MHz, CDCfi) δ 12.06 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.32 - 7.20 (m, 2H), 6.91 - 6.70 (m, 5H), 5.86-5.76 (m, 1H), 4.70 (d, J= 10.0 Hz, 1H), 4.62-4.51 (m, 1H), 3.94 (s, 3H), 2.25 (s, 3H), 1.29 (d, 7= 6.2 Hz, 3H), 1.12 (d, 7= 7.3 Hz, 3H).
452 N\ J'N HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1982; found, 467.1969 1H NMR (400 MHz, CDCfi) δ 12.08 (d, 7= 0.6 Hz, 1H), 8.33 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.31 7.19 (m, 4H), 7.17-7.12 (m, 1H), 7.12 - 7.02 (m, 2H), 6.91 (dd,7=9.3, 8.3 Hz, 1H), 6.86 (d, 7= 5.2 Hz, 1H), 5.77 (dq, 7=10.2, 6.1 Hz, 1H), 4.59 - 4.46 (m, 1H), 3.99 (d,7= 10.2 Hz, 1H), 3.94 (s, 3H), 2.23 (d,7= 1.9 Hz, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ-120.09.
382
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
453 A'\ HRMS-ESI (m/z) ([M+H]+) calcd for C27H29F2N2O6, 515.1993; found, 515.1980 1H NMR (400 MHz, CDCh) δ 12.08 (s, 1H), 8.33 (d,7= 8.0 Hz, 1H), 7.97 (d,7=5.2 Hz, 1H), 7.25 - 7.20 (m, 1H), 7.12-7.01 (m, 2H), 6.93 6.82 (m,2H), 6.57 (td, J= 8.3, 2.5 Hz, 1H), 6.50 (dd,7 = 10.9, 2.5 Hz, 1H), 5.76 (dq, 7= 10.3, 6.1 Hz, 1H), 4.61 -4.48 (m, 1H), 4.45 (d, 7= 10.2 Hz, 1H), 3.94 (s, 3H), 3.77 (s, 3H), 2.22 (d,7 = 1.9 Hz, 3H), 1.22 (d,7= 6.1Hz, 3H), 1.07 (d,7=7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.33, -120.33.
454 & (Thin film) 3373, 2980, 2938, 1735, 1649, 1576, 1528, 1495, 1480, 1451, 1332, 1280, 1263, 1242, 1213, 1144, 1048, 799, 733, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C26H29N2O5, 449.2071; found, 449.2063 1H NMR (400 MHz, CDCh) δ 12.10 (d, 7= 0.6 Hz, 1H), 8.34 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.31 7.27 (m,2H), 7.24-7.15 (m, 4H), 7.15-7.06 (m, 3H), 6.86 (d, 7= 5.2 Hz, 1H), 5.81 (dq,7= 10.2, 6.1Hz, 1H), 4.57 - 4.46 (m, 1H), 4.02 (d, 7= 10.2 Hz, 1H), 3.94 (s, 3H), 2.28 (s, 3H), 1.26 (d,7 = 6.1 Hz, 3H), 0.96 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.68, 168.51, 155.33, 148.70, 141.68, 140.40, 138.15, 136.55, 130.48, 129.48, 128.48, 127.93, 126.59, 109.38, 73.63, 57.57, 56.07, 47.85, 20.98, 19.24, 17.61.
383
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
455 x'X A (Thin film) 3367, 2981, 2938, 1736, 1649, 1576, 1529, 1480, 1451, 1333, 1281, 1263, 1213, 1146, 1048, 801, 734, 700 HRMS-ESI (m/z) ([M+H]+) calcd for C26H29N2O5, 449.2071; found, 449.2068 3H NMR (400 MHz, CDCh) δ 12.11 (d, 7= 0.6 Hz, 1H), 8.35 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.297.24 (m,4H), 7.20-7.15 (m, 3H), 7.03 (d, 7= 7.9 Hz, 2H), 6.86 (d, 7= 5.2 Hz, 1H), 5.80 (dq, 7= 10.1,6.2 Hz, 1H), 4.58- 4.47 (m, 1H), 4.02 (d,7= 10.0 Hz, 1H), 3.94 (s, 3H), 2.25 (s, 3H), 1.25 (d, 7= 6.1 Hz, 3H), 1.01 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.65, 168.50, 155.33, 148.69, 141.41, 140.38, 138.28, 136.20, 130.47, 129.12, 128.74, 128.05, 127.90, 126.82, 109.36, 73.61, 57.44, 56.06, 47.86, 20.92, 19.23, 17.67.
384
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
456 A A A (Thin film) 3369, 2982, 2937, 1735, 1649, 1576, 1528, 1508, 1480, 1451, 1329, 1280, 1263, 1218, 1157, 1049, 815, 800, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1977; found, 467.1974 3H NMR (400 MHz, CDCh) δ 12.09 (s, 1H), 8.34 (d,7= 8.0 Hz, 1H), 7.98 (d,7=5.2 Hz, 1H), 7.25-7.21 (m, 2H), 7.18-7.13 (m, 2H), 7.04 (d, J= 7.9 Hz, 2H), 7.00 -6.92 (m, 2H), 6.86 (d,7= 5.2 Hz, 1H), 5.75 (dq,7 = 9.9, 6.2 Hz, 1H), 4.59-4.47 (m, 1H), 4.02 (d, 7= 9.8 Hz, 1H), 3.94 (s, 3H), 2.26 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.61, 168.52, 161.66 (d, 7= 245.6 Hz), 155.35, 148.71, 140.40, 138.01, 137.20 (d, 7= 3.3 Hz), 136.40, 130.44, 129.53 (d, 7= 7.9 Hz), 129.22, 127.84, 115.57 (d, 7= 21.1 Hz), 109.39, 73.44, 56.56, 56.07, 47.85, 20.92, 19.14, 17.66.
385
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
457 ag (Thin film) 3373, 2982, 2938, 1736, 1649, 1576, 1529, 1509, 1480, 1452, 1330, 1280, 1263, 1242, 1220, 1159, 1048, 815, 799, 732, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C25H26FN2O5, 453.1820; found, 453.1810 'Η NMR (300 MHz, CDCh) δ 12.07 (d,/= 0.6 Hz, 1H), 8.33 (d,/= 8.0 Hz, 1H), 7.98 (d,/= 5.2 Hz, 1H), 7.337.19 (m, 7H), 6.96-6.88 (m, 2H), 6.87 (dd,/= 5.3, 0.6 Hz, 1H), 5.78 (dq,/=9.9, 6.1Hz, 1H), 4.61-4.47 (m, 1H), 4.05 (d,/= 10.0 Hz, 1H), 3.94 (s, 3H), 1.26 (d,/ = 6.2 Hz, 3H), 1.05 (d,/= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.62, 168.57, 161.59 (d,/= 245.2 Hz), 155.38, 148.73, 140.92, 140.43, 137.11 (d,/= 3.5 Hz), 130.39, 129.53 (d,/ = 7.8 Hz), 128.88, 127.99, 127.08, 115.29 (d,/= 21.2 Hz), 109.43, 73.50, 57.03, 56.08, 47.87, 19.21, 17.69.
386
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
458 (Thin film) 3366, 2979, 2939, 1736, 1649, 1576, 1529, 1509, 1481, 1451, 1332, 1264, 1242, 1220, 1159, 1049, 815, 800, 770, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C26H28FN2O5, 467.1977; found, 467.1969 'Η NMR (300 MHz, CDCh) δ 12.08 (d, 7= 0.6 Hz, 1H), 8.33 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.307.21 (m,2H), 7.14 (d, 7= 8.3 Hz, 2H), 7.09 (d, 7= 8.2 Hz, 2H), 6.95 - 6.84 (m, 3H), 5.76 (dq, 7= 10.1,6.1 Hz, 1H), 4.59-4.47 (m, 1H), 4.01 (d,7= 10.1 Hz, 1H), 3.94 (s, 3H), 2.29 (s, 3H), 1.25 (d,7=6.1 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 171.61, 168.55, 161.53 (d, 7= 244.9 Hz), 155.37, 148.71, 140.41, 137.93, 137.41 (d, 7= 3.3 Hz), 136.72, 130.39, 129.54, 129.41 (d, 7= 7.9 Hz), 127.82, 115.24 (d, 7 = 21.3 Hz), 109.41, 73.55, 56.67, 56.07, 47.87, 20.96, 19.20, 17.68.
387
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
459 NA X (Thin film) 3376, 2984, 2938, 1737, 1649, 1576, 1529, 1503, 1481, 1452, 1327, 1281, 1263, 1243, 1212, 1146, 1050, 966, 849, 800, 733, 699 HRMS-ESI (m/z) ([M+H]+) calcd for C25H25F2N2O5, 471.1726; found, 471.1726 1H NMR (400 MHz, CDCR) δ 12.07 (d, 7= 0.6 Hz, 1H), 8.32 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.357.20 (m, 5H), 7.19-7.10 (m, 1H), 6.88 - 6.75 (m, 3H), 5.88-5.77 (m, 1H), 4.584.47 (m, 1H), 4.42 (d,7= 10.1 Hz, 1H), 3.94 (s, 3H), 1.29 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCb) δ 171.56, 168.54, 162.05 (dd,7= 172.5, 11.9 Hz), 161.09- 159.28 (m), 155.35, 148.72, 140.42, 140.02, 130.41, 130.23129.63 (m), 128.61, 128.18, 127.03, 124.46- 123.89 (m), 111.63 (d,7=21.2Hz), 109.41, 104.54- 103.81 (m), 72.76, 56.08, 49.36, 47.83, 18.90, 17.60.
388
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
460 w A A (Thin film) 3370, 2983, 2937, 1737, 1649, 1576, 1529, 1502, 1481, 1452, 1439, 1329, 1281, 1264, 1243, 1211, 1147, 1050, 966, 849, 801, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C26H27F2N2O5, 485.1883; found, 485.1880 1H NMR (400 MHz, CDCI3) δ 12.08 (d, 7= 0.6 Hz, 1H), 8.33 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.267.21 (m, 1H), 7.20-7.15 (m, 2H), 7.07 - 7.01 (m, 2H), 6.88-6.85 (m, 1H), 6.846.74 (m, 2H), 5.86 - 5.72 (m, 1H), 4.59-4.48 (m, 1H), 4.39 (d, 7= 9.9 Hz, 1H), 3.94 (s, 3H), 2.26 (s, 3H), 1.28 (d, 7= 6.3 Hz, 3H), 1.04 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 171.55, 168.53, 161.99 (dd, 7 = 171.0, 11.9 Hz), 160.02 (dd, 7= 170.8, 11.7 Hz), 155.36, 148.72, 140.41, 136.92, 136.63, 130.43, 129.97- 129.69 (m), 129.24, 128.06, 124.73 - 124.42 (m), 111.58 (d, 7= 17.7 Hz), 109.40, 104.83 103.37 (m), 72.82, 56.08, 48.91, 47.85, 20.95, 18.90, 17.67.
389
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
461 QR A A (Thin film) 3371,2984, 2939, 1738, 1649, 1604, 1577, 1529, 1503, 1481, 1452, 1439, 1326, 1281, 1264, 1242, 1223, 1160, 1050, 966, 849, 810, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C25H24F3N2O5, 489.1632; found, 489.1624 1H NMR (400 MHz, CDCfi) δ 12.05 (d, 7= 0.6 Hz, 1H), 8.30 (d, 7= 8.0 Hz, 1H), 7.98 (d, 7= 5.2 Hz, 1H), 7.317.17 (m, 3H), 6.97-6.75 (m, 5H), 5.83 - 5.73 (m, 1H), 4.59 - 4.49 (m, 1H), 4.40 (d, 7= 10.0 Hz, 1H), 3.95 (s, 3H), 1.28 (d, 7= 6.1 Hz, 3H), 1.08 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 171.51, 168.59, 162.96- 162.09 (m), 161.43 - 159.21 (m), 155.41, 148.74, 140.45, 135.75, 130.33, 129.73 (d, 7= 8.0 Hz), 124.13 (dd,7= 15.2, 3.7Hz), 115.43 (d,7=21.3 Hz), 111.73 (d, 7= 25.0 Hz), 109.46, 104.30 (t, 7= 25.8 Hz), 72.66, 56.10, 48.70, 47.86, 18.91, 17.67.
390
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
462 γ NS HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1931; found, 543.1937. 1Η NMR (400 MHz, CDCh) 6 8.28 (d, 7= 5.4 Hz, 1H), 8.14 (d, 7= 7.8 Hz, 1H), 7.26 -7.15(m, 4H), 6.94 (dddd,7 = 24.3, 8.7,6.9, 2.1Hz, 5H), 5.76-5.63 (m, 3H), 4.55 (p, 7= 7.3 Hz, 1Η), 4.05 (d,7= 8.9 Hz, 1Η), 3.92 (s, 3H), 2.06 (s, 3H), 1.32 (d,7=7.1 Hz, 3H), 1.22 (d, 7= 6.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 171.92, 170.28, 162.91, 162.81, 162.77, 160.46, 160.37, 145.63, 144.13, 142.28, 136.93, 136.90, 136.54, 136.51, 129.82, 129.74, 129.70, 129.62, 115.72, 115.51, 115.43, 115.22, 109.60, 89.60, 73.10,56.20,55.58, 48.04, 20.85,20.81, 18.94, 18.05.
391
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
463 A NS A HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1931; found, 543.1937. XH NMR (400 MHz, CDCh) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.20 (d, 7= 7.9 Hz, 1H), 7.28 -7.17(m, 4H), 7.02-6.89 (m, 5H), 5.76-5.66 (m, 3H), 4.55 (p, 7= 7.3 Hz, 1H), 4.04 (d, 7= 9.7 Hz, 1H), 3.90 (s, 3H), 2.05 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.24, 170.26, 162.95, 162.90, 162.86, 160.51, 160.42, 160.28, 145.68, 143.98, 142.41, 136.94, 136.91, 136.86, 136.82, 129.62, 129.57, 129.54, 129.49, 115.79, 115.58, 115.49, 115.28, 109.58, 89.51,73.04, 56.18, 56.13,48.05,20.85, 19.14, 17.81.
392
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
464 ee (Thin film) 3378, 2984, 1738, 1676, 1496, 1202, 1003, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O7, 571.2250; found, 571.2265 3H NMR (400 MHz, CDCfi) 6 8.26 (d, 7= 5.3 Hz, 1H), 8.21 (d, 7= 7.9 Hz, 1H), 7.26 -7.22(m, 1H), 7.14 (dd, 7= 8.6, 5.8 Hz, 1H), 6.94 (d,7 = 5.4 Hz, 1H), 6.89-6.77 (m, 4H), 5.73 (s, 2H), 5.62 (dq, 7 = 9.7, 6.2 Hz, 1H), 4.56 (p, 7 = 7.2 Hz, 1H), 4.44 (d,7= 9.8 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H), 2.06 (s, 3H), 1.30 (d, 7= 6.2 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCfi) δ 172.30, 170.26, 162.91, 161.19 (d, 7= 245.6 Hz), 161.10 (d, 7= 245.0 Hz), 160.28, 145.70, 143.98, 142.43, 139.12 (d, 7= 7.4 Hz), 138.81 (d, 7= 7.5 Hz), 134.89 (d, 7= 3.3 Hz), 134.39 (d, 7= 3.2 Hz), 129.37 (d, 7= 8.2 Hz), 128.75 (d, 7= 8.3 Hz), 117.41 (d, 7= 20.9 Hz), 117.10 (d, 7= 20.9 Hz), 112.94 (d, 7= 20.9 Hz), 112.63 (d, 7= 20.8 Hz), 109.59, 89.52, 74.29, 56.19, 48.07, 46.40, 20.86, 20.20, 20.12, 18.82, 17.86. 19F NMR (376 MHz, CDCfi) δ-116.57, -117.03.
393
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
465 (Thin film) 3379, 2962, 1737, 1676, 1506, 1201, 1004, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C36H47N2O7, 619.3378; found, 619.3388 3H NMR (400 MHz, CDCh) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 7.32 -7.20 (m, 8H), 6.93 (d,7= 5.4 Hz, 1H), 5.79 (dq,7 = 10.2, 6.1 Hz, 1H), 5.73 5.70 (m,2H), 4.50 (p, 7= 7.2 Hz, 1H), 3.98 (d, 7= 10.2 Hz, 1H), 3.89 (s, 3H), 2.05 (s, 3H), 1.27- 1.22 (m, 21H), 0.78 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.43, 170.23, 162.84, 160.24, 149.56, 149.37, 145.69, 143.91, 142.62, 138.80, 138.26, 127.69, 127.65, 125.60, 125.33, 109.49, 89.55, 73.71, 57.25,56.15,48.04,34.36, 34.31,31.30, 20.85, 19.34, 17.50.
394
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
466 S' (Thin film) 3378, 2959, 1737, 1676, 1506, 1202, 1044, 1004, 828, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C34H43N2O7, 591.3065; found, 591.3077 1Η NMR (400 MHz, CDCh) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.22 (d, 7= 7.8 Hz, 1H), 7.28 -7.19(m, 4H), 7.16-7.06 (m,4H), 6.93 (d, 7= 5.4 Hz, 1H), 5.78 (dq, 7=10.2, 6.1 Hz, 1H), 5.72 (d, 7= 0.9 Hz, 2H), 4.51 (p, 7= 7.2 Hz, 1H), 3.98 (d, 7= 10.2 Hz, 1H), 3.89 (s, 3H), 2.81 (dh, 7 = 10.6, 6.9 Hz, 2H), 2.05 (s, 3H), 1.24 (d, 7= 6.1 Hz, 3H), 1.18 (dd, 7= 13.6, 6.9 Hz, 12H), 0.81 (d, 7=7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.42, 170.24, 162.85, 160.24, 147.29, 147.13, 145.69, 143.92, 142.63, 139.19, 138.71, 127.95, 127.92, 126.75, 126.48, 109.49, 89.55, 73.66, 57.39,56.16, 48.05,33.65, 33.61,23.99, 23.97, 23.93, 20.86, 19.33, 17.57.
395
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
467 ¥ (Thin film) 3388, 2979, 1756, 1677, 1503, 1203, 1044, 1004, 970, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O7, 563.2752; found, 563.2764 1H NMR (400 MHz, CDCh) 6 8.27 (d,/= 5.3 Hz, 1H), 8.23 (d,/= 7.8 Hz, 1H), 7.07 -6.90 (m, 7H), 5.82-5.67 (m, 3H), 4.54 (p,/= 7.2 Hz, 1H), 3.90 (s, 3H), 2.17 (t,/ = 11.4 Hz, 12H), 2.06 (s, 3H), 1.28- 1.20 (m, 4H), 0.93 (d, /= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.41, 170.25, 162.84, 160.23, 145.69, 143.90, 142.67, 139.25, 139.11, 136.78, 136.34, 134.93, 134.51, 129.90, 129.62, 129.39, 129.38, 125.30, 125.08, 109.48, 89.55,73.49,57.11,56.16, 48.12, 20.86, 19.87, 19.80, 19.32, 19.29, 19.24, 17.80.
468 SN Ss ESIMS m/z 541.2 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 8.41 (d,/= 7.7 Hz, 1H), 8.30 (d,/= 5.4 Hz, 1H), 7.32 -7.21 (m, 1H), 7.14 (dd,/ = 8.5, 5.8 Hz, 1H), 6.99 (d,/= 5.5 Hz, 1H), 6.83 (ddd,/= 15.6, 10.1, 7.6 Hz, 4H), 5.62 (dq,/= 9.6, 6.1Hz, 1H), 4.62-4.50 (m, 1H), 4.43 (d, /= 9.7 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 2.36 (s, 3H), 2.31 (s, 3H), 1.29 (d,/= 6.2 Hz, 3H), 1.03 (d,/= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-116.52, -116.96.
396
2019201931 20 Mar 2019
Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
469 •X o (Thin film) 3379, 2962, 1772, 1677, 1508, 1198, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C35H45N2O6, 589.3272; found, 589.3289 1H NMR (400 MHz, CDCh) 6 8.43 (d, 7= 7.9 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 7.26 (d, 7= 12.1 Hz, 8H), 6.98 (d, 7= 5.4 Hz, 1H), 5.78 (dq,7= 10.1, 6.1Hz, 1H), 4.564.43 (m, 1H), 3.97 (d,7= 10.2 Hz, 1H), 3.88 (s, 3H), 2.37 (s, 3H), 1.25 (d,7= 12.6 Hz, 21H), 0.77 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.32, 168.88, 162.23, 159.40, 149.55, 149.37, 146.64, 141.60, 138.76, 138.25, 137.43, 127.70, 127.65, 125.60, 125.32, 109.67, 73.75, 57.22, 56.25,47.81,34.35,34.31, 31.31,31.30, 20.73, 19.32, 17.69.
397
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
470 §5 (Thin film) 3379, 2960, 1772, 1677, 1509, 1201, 1175, 1047, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C33H41N2O6, 561.2959; found, 561.2977 3H NMR (400 MHz, CDCh) 6 8.42 (d, 7= 7.6 Hz, 1H), 8.32 (d, 7= 5.5 Hz, 1H), 7.22 (dd, 7= 8.3, 2.5 Hz, 4H), 7.15-7.04 (m, 4H), 6.98 (d, 7= 5.5 Hz, 1H), 5.78 (dq,7= 10.1, 6.1Hz, 1H), 4.544.43 (m, 1H), 3.97 (d,7= 10.2 Hz, 1H), 3.89 (s, 3H), 2.82 (dp, 7= 11.9, 6.9 Hz, 2H),2.37(s, 3H), 1.23 (d,7 = 6.2 Hz, 3H), 1.18 (dd, 7= 14.7, 6.9 Hz, 12H), 0.80 (d,7 = 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.31, 168.89, 162.23, 159.41, 147.28, 147.13, 146.64, 141.61, 139.14, 138.70, 137.43, 127.96, 127.92, 126.75, 126.47, 109.68, 73.70, 57.36, 56.25,47.83,33.64,33.61, 23.97, 23.93,20.74, 19.31, 17.75.
471 ••Ά sc CN (Thin film) 3379, 2978, 1771, 1676, 1505, 1450, 1310, 1199, 1050, 907, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O6, 533.2646; found, 533.2659 3H NMR (400 MHz, CDCh) δ 8.48 - 8.37 (m, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 7.096.90 (m, 7H), 5.74 (dq,7= 10.0, 6.1Hz, 1H), 4.584.46 (m, 1H), 3.98-3.83 (m, 4H), 2.38 (s, 3H), 2.17 (dd, 7 = 12.4, 11.0 Hz, 12H), 1.22 (d, 7= 6.1 Hz, 3H), 0.92 (d, 7=7.1 Hz, 3H).
398
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
472 >V\ Ax (Thin film) 3382, 2982, 1737, 1677, 1501, 1202 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O9, 603.2149; found, 603.2163 1H NMR (400 MHz, CDC13) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.22 (d, 7= 7.9 Hz, 1H), 7.38 (m, 1H), 7.13 (m, 1H), 6.94 (d, 7= 5.4 Hz, 1H), 6.616.47 (m, 4H), 5.87 (dq,7= 9.7, 6.2 Hz, 1H), 5.72 (s, 2H), 4.84 (d, 7= 9.6 Hz, 1H), 4.64 - 4.48 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 1.03 (d, 7= 7.2 Hz, 3H).
473 1 (Thin film) 3367, 2985, 1749, 1694, 1506, 1201, 1130, 828 HRMS-ESI (m/z) ([M+H]+) calcd for C28H26F5N2O7, 597.1655; found, 597.1672 1H NMR (400 MHz, CDC13) δ 8.77-8.42 (m, 1H), 8.428.15 (m, 1H), 7.26-7.15 (m, 4H), 7.06 - 6.86 (m, 5H), 5.84-5.66 (m, 3H), 5.375.19 (m, 1H), 4.13-4.03 (m, 1H), 4.04-3.83 (m, 3H), 2.09- 1.99 (m, 3H), 1.301.16 (m, 3H).
399
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
474 NS Y γ > HRMS-ESI (m/z) ([M+H]+) calcd for C29H33N2O7, 521.2282; found, 521.2292. 3H NMR (300 MHz, CDC13) δ 8.28 (t, J= 7.2 Hz, 2H), 7.35-7.12 (m, 10H), 6.94 (d, 7= 5.4 Hz, 1H), 5.86 (q, 7= 6.3 Hz, 1H), 5.75-5.68 (m,2H), 4.62 (p, 7= 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.75 (s, 3H), 1.16 (d, 7 = 6.3 Hz, 3H), 1.12 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.27, 170.20, 162.88, 160.26, 146.57, 145.66, 145.11, 143.98, 142.56, 128.18, 128.09, 127.92, 127.40, 126.28, 126.11, 109.53, 89.54, 75.94, 56.17, 50.41,48.23,23.95, 20.84, 18.13, 15.97.
475 Sx 'S (Thin film) 3379, 2940, 1769, 1736, 1677, 1598, 1500, 1277, 1192, 1174, 1151, 1033, 953 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2055 3H NMR (400 MHz, CDCI3) δ 8.41 (d, 7= 4.6 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.37 (dd, 7= 8.5, 6.7 Hz, 1H), 7.12 (dd, 7= 8.3, 6.7 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.63 - 6.44 (m, 4H), 5.86 (dq, 7=9.5, 6.2 Hz, 1H), 4.83 (d, 7= 9.5 Hz, 1H), 4.62 - 4.45 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 1.21 (d, 7= 6.2 Hz, 3H), 1.01 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-113.49, -113.81.
400
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
476 A Nr AS (Thin film) 3382, 3028, 2984, 1736, 1677, 1498, 1451, 1436, 1310, 1201, 1043, 967, 910, 829, 728, 703 HRMS-ESI (m/z) ([M+H]+) calcd for C28H31N2O7, 507.2126; found, 507.2141 1:1 mixture of diastereomers. A NMR (500 MHz, CDCh) δ 8.52-8.46 (m, 1H), 8.20 (d, 7= 7.6 Hz, 1H), 8.16 (d, J= 7.5 Hz, 1H), 7.33-7.10 (m, 11H), 5.86-5.74 (m, 3H), 4.61-4.48 (m, 1H), 4.10-4.04 (m, 1H), 4.02 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H), 1.31 (d, 7= 7.1 Hz, 3H), 1.28- 1.20 (m, 3H), 0.91 (d, 7= 7.2 Hz, 3H).
477 A A (Thin film) 3376, 2985, 2228, 1769, 1738, 1674, 1505 HRMS-ESI (m/z) ([M+H]+) calcd for C29H27N4O6, 527.1925; found, 527.1931 A NMR (400 MHz, CDCh) δ 8.30 (d, 7= 5.5 Hz, 1H), 7.60 (d, 7= 8.3 Hz, 2H), 7.54 (d, 7= 8.3 Hz, 2H), 7.417.30 (m,4H), 7.03 (d,7=5.5 Hz, 1H), 5.76 (dq, 7=8.8, 6.1Hz, 1H), 4.60-4.52 (m, 1H), 4.20 (d, 7= 9.0 Hz, 1H), 3.95 (d, 7= 9.9 Hz, 1H), 3.92 (s, 3H), 2.39 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.08 (d, 7= 7.2 Hz, 3H)
478 A (Thin film) 3387, 2986, 1772, 1739, 1677, 1617, 1509 HRMS-ESI (m/z) ([M+H]+) calcd for C29H27F6N2O6, 613.1768; found, 613.178 A NMR (400 MHz, CDCh) δ 8.38 (d, 7= 7.9 Hz, 1H), 8.32-8.29 (m, 1H), 7.56 (d, 7= 7.9 Hz, 2H), 7.52 (d,7= 8.5 Hz, 2H), 7.44-7.36 (m, 4H), 7.01 (dd, 7= 5.5, 3.5 Hz, 1H), 5.88 - 5.79 (m, 1H), 4.59-4.53 (m, 1H), 4.22 (d, 7= 9.2 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.28- 1.22 (m, 3H), 0.98 (d,7=7.2 Hz, 3H).
401
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
479 ''Y (Thin film) 3379, 2980, 1772, 1714, 1678, 1508 HRMS-ESI (m/z) ([M+H]+) calcd for C33H37N2O10, 621.2443; found, 621.2451 1H NMR (400 MHz, CDCfi) δ 8.38 (d, J= 8.7 Hz, 1H), 8.32-8.29 (m, 1H), 7.97 (d, J= 8.3 Hz, 2H), 7.93 (d,7= 8.2 Hz, 2H), 7.38 (d, 7= 8.3 Hz, 2H), 7.34 (d, 7= 8.4 Hz, 2H), 7.00 (d, 7= 5.5 Hz, 1H), 5.85 (dq, 7= 9.6, 6.1 Hz, 1H), 4.59-4.50 (m, 1H), 4.38-4.30 (m, 4H), 4.21 (d, 7= 9.7 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.36 (t, 7= 7.3 Hz, 6H), 1.25 (d,7= 6.3 Hz, 3H), 0.98 (d,7=7.1 Hz, 3H).
480 (Thin film) 3379, 2983, 1714, 1676, 1607, 1507 HRMS-ESI (m/z) ([M+H]+) calcd for C34H39N2O11, 651.2548; found, 651.2560 1H NMR (400 MHz, CDCfi) δ 8.28 - 8.24 (m, 1H), 8.20 (d, 7= 7.8 Hz, 1H), 8.007.92 (m,4H), 7.42-7.31 (m, 4H), 6.95 (d, 7= 5.4 Hz, 1H), 5.85 (dp, 7= 9.4, 7.2, 6.6 Hz, 1H), 5.73-5.67 (m, 2H), 4.56 (p, 7= 6.9 Hz, 1H), 4.39 - 4.28 (m, 4H), 4.22 (d, 7= 9.7 Hz, 1H), 3.91 (d,7= 1.5 Hz, 3H), 2.06 (s, 3H), 1.37 (t, 7= 7.2 Hz, 6H), 1.27 (d, 7= 6.2 Hz, 3H), 0.98 (d, 7= 7.1 Hz, 3H).
402
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
481 >'V (Thin film) 3379, 2939, 1737, 1677, 1490, 1247, 1202, 1033 HRMS-ESI (m/z) ([M+Na]+) calcd for C30H32Cl2N2NaO9, 657.1377; found, 657.1387 1H NMR (400 MHz, CDC13) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.22 (d, 7= 7.9 Hz, 1H), 7.34 (d, 7= 8.3 Hz, 1H), 7.09 (d, 7= 8.0 Hz, 1H), 6.94 (d,7= 5.4 Hz, 1H), 6.88-6.82 (m, 2H), 6.81 (s, 1H), 6.76 (d,7 = 2.0 Hz, 1H), 5.86 (dq,7= 9.7, 6.2 Hz, 1H), 5.72 (s, 2H), 4.84 (d, 7= 9.6 Hz, 1H), 4.57 (p, 7= 7.2 Hz, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H).
482 A (Thin film) 3380, 2981, 1736, 1677, 1597, 1500, 1274, 1202, 1003 HRMS-ESI (m/z) ([M+H]+) calcd for C32H37F2N2O9, 631.2462; found, 631.2461 1H NMR (400 MHz, CDC13) δ 8.25 (t, 7= 6.6 Hz, 2H), 7.34 (dd,7=8.5, 6.9 Hz, 1H), 7.13 (td, 7=7.9, 6.7, 4.7 Hz, 1H), 6.93 (d,7=5.4 Hz, 1H), 6.60-6.36 (m, 4H), 5.90 (dq, 7=10.2, 6.2 Hz, 1H), 5.73 (s, 2H), 4.83 (d,7= 10.1 Hz, 1H), 4.634.48 (m, 1H), 4.08-3.79 (m, 7H), 2.06 (s, 3H), 1.47 (t, 7 = 6.9 Hz, 3H), 1.40 (t, 7= 6.9 Hz, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDC13) δ-113.76, -114.20.
403
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
483 (Thin film) 3378, 2980, 1736, 1677, 1591, 1491, 1247, 1201, 1040 HRMS-ESI (m/z) ([M+H]+) calcd for C32H37CI2N2O9, 663.1871; found, 663.1877 1H NMR (400 MHz, CDC13) δ 8.29-8.19 (m, 2H), 7.31 (d,/= 8.3 Hz, 1H), 7.11 (d, /= 8.2 Hz, 1H), 6.94 (d,/= 5.4 Hz, 1H), 6.86-6.73 (m, 3H), 6.72 (d,/= 2.0 Hz, 1H), 5.89 (dq,/= 9.9, 6.2 Hz, 1H), 5.73 (s, 2H), 4.83 (d,/= 9.8 Hz, 1H), 4.57 (p, /= 7.2 Hz, 1H), 4.05-3.83 (m, 7H), 2.06 (s, 3H), 1.47 (t, /= 6.9 Hz, 3H), 1.39 (t,/= 6.9 Hz, 3H), 1.23 (d,/= 6.1 Hz, 3H), 1.06 (d,/= 7.2 Hz, 3H).
484 >V\ (Thin film) 3378, 2978, 1758, 1734, 1676, 1504, 1200, 1043 HRMS-ESI (m/z) ([M+H]+) calcd for C34H43N2O9, 623.2963; found, 623.2962 1H NMR (400 MHz, CDC13) δ 8.29-8.18 (m, 2H), 7.30 (d,/= 7.8 Hz, 1H), 7.13 (d, /= 7.7 Hz, 1H), 6.92 (d,/= 5.4 Hz, 1H), 6.67-6.57 (m, 3H), 6.54 (s, 1H), 5.93 (dq, / = 10.3, 6.1 Hz, 1H), 5.72 (s, 1H), 5.72 (s, 1H), 4.90 (d,/ = 10.1 Hz, 1H), 4.55 (p,/= 7.1Hz, 1H), 4.04-3.81 (m, 7H), 2.26 (s, 3H), 2.23 (s, 3H), 2.05 (d,/= 1.8 Hz, 3H), 1.47 (t,/= 7.0 Hz, 3H), 1.39 (t,/= 7.0 Hz, 3H), 1.23 (d,/= 6.1 Hz, 3H), 0.99 (d, /= 7.2 Hz, 3H).
404
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
485 vS HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2051; found, 573.2044 1H NMR (400 MHz, CDCh) δ 8.39 (d, J= 6.9 Hz, 1H), 8.29 (d, J= 5.4 Hz, 1H), 7.05 -6.92(m, 3H), 6.89 (dd,7= 8.1,2.1Hz, 1H), 6.82 (dddd, 7= 15.8, 8.3, 4.0, 2.1 Hz, 3H), 5.72 (dq, 7= 9.7, 6.1 Hz, 1H), 4.65 - 4.48 (m, 1H), 3.99 (d, 7= 9.8 Hz, 1H), 3.88 (s, 3H), 3.85 (s, 6H), 2.38 (s, 3H), 1.24 (d, 7= 6.1 Hz, 3H), 1.02 (d, 7= 7.1 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-137.20, -137.68.
405
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
486 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2542; found, 565.2535 3H NMR (400 MHz, CDC13) 6 8.43 (d, 7= 7.8 Hz, 1H), 8.28 (d, 7= 5.4 Hz, 1H), 7.21 (d, 7= 8.5 Hz, 1H), 7.177.09 (m, 1H), 6.96 (d,7=5.5 Hz, 1H), 6.79 - 6.57 (m, 4H), 5.63 (dq, 7=9.7, 6.1Hz, 1H), 4.64 - 4.50 (m, 1H), 4.38 (d, 7= 9.9 Hz, 1H), 3.86 (s, 3H), 3.73 (s, 3H), 3.71 (s, 3H), 2.38 (s, 3H), 2.35 (s, 3H), 2.31 (s, 3H), 1.29 (d,7 = 6.1 Hz, 3H), 1.01 (d, 7= 7.1Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.25, 168.81, 162.28, 159.43, 157.80, 157.67, 146.63, 141.55, 137.98, 137.71, 137.44, 131.95, 131.46, 128.85, 128.22, 116.24, 116.03, 111.25, 110.94, 109.75, 74.80, 56.24, 55.05, 47.92, 46.23,20.71,20.36, 20.28, 18.88, 18.08.
487 SN NS A HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O9, 603.2157; found, 603.2150 1H NMR (400 MHz, CDCI3) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.21 (d, 7= 7.8 Hz, 1H), 7.06 - 6.92 (m, 3H), 6.92 - 6.74 (m,4H), 5.84-5.61 (m, 3H), 4.56 (p, 7= 7.3 Hz, 1H), 4.00 (d, 7= 9.8 Hz, 1H), 3.91 (s, 3H), 3.86 (s, 6H), 2.06 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCf) δ-137.20, -137.72.
406
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
488 A (Thin film) 3383,2938, 2837, 1770, 1733, 1677, 1609, 1586, 1505, 1453 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O10, 597.2443; found, 597.2438 1H NMR (500 MHz, CDCfi) 6 8.44 (s, 1H), 8.31 (d,7= 5.4 Hz, 1H), 7.33 (d,7=8.5 Hz, 1H), 7.10 (d, J= 8.4 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.42 - 6.34 (m, 4H), 5.85 (dq, 7=9.7, 6.2 Hz, 1H), 4.81 (d, 7= 9.8 Hz, 1H), 4.59-4.49 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 1.21 (d, 7= 6.2 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H).
489 A A (Thin film) 3382, 2937, 1771, 1733, 1677, 1572, 1505, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2541 1H NMR (500 MHz, CDCfi) 6 8.44 (s, 1H), 8.31 (d,7= 5.4 Hz, 1H), 7.31 (d,7=7.7 Hz, 1H), 7.10 (d, 7= 8.1 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.69 - 6.65 (m, 1H), 6.65 - 6.62 (m, 2H), 6.60 6.54 (m, 1H), 5.89 (dq,7= 9.8, 6.2 Hz, 1H), 4.90 (d,7= 9.8 Hz, 1H), 4.58-4.48 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.21 (d, 7= 6.2 Hz, 3H), 0.95 (d, 7= 7.2 Hz, 3H).
407
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
490 'N· A (Thin film) 3383,2937, 2836, 1772, 1735, 1678, 1502, 1453 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2538 1H NMR (500 MHz, CDC13) 6 8.45 (s, 1H), 8.32 (d,7= 5.4 Hz, 1H), 7.22 (d,7=2.1 Hz, 1H), 7.03 (d, 7= 2.2 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.93 (ddd, 7= 8.3, 2.3, 0.8 Hz, 1H), 6.89 (ddd, 7 = 8.2, 2.2, 0.8 Hz, 1H), 6.73 (d, 7= 8.3 Hz, 1H), 6.67 (d,7= 8.2 Hz, 1H), 5.85 (dq,7 = 10.0, 6.2 Hz, 1H), 4.95 (d,7 = 10.0 Hz, 1H), 4.58-4.46 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.72 (s, 3H),2.38(s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.22 (d, 7= 6.1 Hz, 3H), 0.95 (d, 7= 7.1 Hz, 3H).
491 k (Thin film) 3382, 2985, 2941,2840, 1771, 1736, 1677, 1578, 1508, 1479 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2042 1H NMR (500 MHz, CDCI3) for both isomers of a 1:1 mixture of diastereomers d 8.40 (s, 1H), 8.38 (s, 1H), 8.32 (d, 7= 5.0 Hz, 1H), 8.31 (d, 7= 5.3 Hz, 1H), 7.21- 7.13 (m,2H), 7.03 -6.83 (m, 12H), 5.76-5.63 (m, 2H), 5.04 (d, 7= 11.9 Hz, 1H), 5.02 (d, 7= 11.2 Hz, 1H), 4.63-4.47 (m, 2H), 3.93 (d, 7= 2.0 Hz, 3H), 3.92 (s, 3H), 3.91-3.89 (m, 6H), 3.80 (d, 7= 1.7 Hz, 3H), 3.76 (d,7= 1.6 Hz, 3H),2.39(s, 3H), 2.38 (s, 3H), 1.31 (d,7=7.2 Hz, 3H), 1.29- 1.22 (m, 6H), 1.03 (d, 7= 7.2 Hz, 3H).
408
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
492 os Ό A (Thin film) 3383,2941, 2839, 1770, 1736, 1677, 1592, 1495 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2045 1H NMR (500 MHz, CDC13) for the major isomer of a 2:1 mixture of diastereomers d 8.44 (s, 1H), 8.32 (d,7=5.5 Hz, 1H), 7.18 (dd, J= 9.7, 3.0 Hz, 1H), 6.99 (d,7=5.5 Hz, 1H), 6.96 (dd, 7=9.5, 3.0 Hz, 1H), 6.87-6.79 (m, 2H), 6.76 (dd, J= 9.0, 4.6 Hz, 1H), 6.72 (d, 7= 4.6 Hz, 1H), 5.87 (dq, 7= 9.6, 6.2 Hz, 1H), 4.88 (d, 7= 9.6 Hz, 1H), 4.60-4.53 (m, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 2.38 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H).
409
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
493 NS Ύ SS A HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O11, 627.2548; found, 627.2546 3H NMR (500 MHz, CDCh) for 1:1 mixture of diastereomers δ 8.26 (t, J = 5.1Hz, 4H), 7.07 (ddd, 7 = 13.9, 7.9, 1.1 Hz, 2H), 7.006.89 (m,6H), 6.85 (td, 7= 8.8, 8.0, 1.3 Hz, 2H), 6.78- 6.72 (m, 4H), 5.75 - 5.71 (m, 4H), 5.71 - 5.62 (m, 2H), 5.12 (dd, 7= 13.7, 9.8 Hz, 2H), 4.63 - 4.47 (m, 2H), 3.91 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.06 (s, 6H), 1.32 (d,7=7.1 Hz, 3H), 1.26 (d, 7= 6.0 Hz, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) for 1:1 mixture of diastereomers δ 172.36, 171.98, 170.28, 162.82, 162.78, 160.26, 160.23, 152.82, 152.78, 152.71, 147.42, 147.31, 147.19, 147.11, 145.68, 143.95, 143.93, 142.70, 142.64, 135.14, 134.87, 134.78, 134.61, 123.66, 123.62, 121.05, 120.97, 120.46, 120.33, 110.74, 110.61, 110.55, 109.44, 99.98, 89.63, 89.59, 73.81,73.75,60.40, 60.36, 60.31,60.25,56.17, 56.16, 55.64, 55.59, 48.18, 48.12,41.96,41.83,29.28, 20.88, 18.86, 18.71, 18.41, 17.91.
410
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
494 A HRMS-ESI (m/z) ([M+H]+) calcd for C34H43N2O11, 655.2861; found, 655.2858 XH NMR (500 MHz, CDCh) for 1:1 mixture of diastereomers δ 8.40 - 8.28 (m, 2H), 8.26 (dd, 7=5.3, 3.7 Hz, 2H), 7.07 (ddd, 7 = 13.1,8.0, 1.2 Hz, 2H), 7.036.89 (m,6H), 6.88-6.80 (m, 2H),6.75(td,7=5.6, 2.8 Hz, 4H), 5.81 -5.72 (m, 4H), 5.72 - 5.62 (m, 2H), 5.12 (dd, 7= 13.4, 9.8 Hz, 2H), 4.54 (dp, 7= 17.6, 7.2 Hz, 2H), 3.89 (s, 3H), 3.89 (s, 3H), 3.88 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.54 (pd, 7= 7.0, 4.2 Hz, 2H), 1.32 (d, 7= 7.1 Hz, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.14 (d, 7= 3.1 Hz, 6H), 1.13 (d, 7= 3.1 Hz, 6H), 1.00 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) for 1:1 mixture of diastereomers δ 176.26, 176.24, 172.37, 171.99, 162.79, 162.73, 160.25, 160.21, 152.82, 152.78, 152.70, 147.42, 147.32, 147.19, 147.11, 145.53, 144.22, 144.16, 142.27, 135.14, 134.88, 134.79, 134.62, 123.66, 123.62, 121.06, 120.97, 120.47, 120.33, 110.76, 110.74, 110.61, 110.55, 109.39, 99.98, 90.02, 89.95, 73.79, 73.73,60.40, 60.36, 60.31, 60.26, 56.12, 56.10, 55.64, 55.59, 48.18, 48.12,41.96, 41.82,33.87,33.85, 18.85, 18.68, 18.41, 17.91.
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
495 A HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O10, 597.2443; found, 597.2434 1H NMR (500 MHz, CDCR) for 1:1 mixture of diastereomers δ 8.45 (s, 2H), 8.32 (d, J= 3.9 Hz, 1H), 8.31 (d, 7= 3.9 Hz, 1H), 7.07 (ddd, 7= 12.2, 8.0, 1.3 Hz, 2H), 7.01 - 6.89 (m, 6H), 6.89-6.79 (m, 2H), 6.75 (td, 7=6.8, 1.5 Hz, 4H), 5.735.60 (m,2H), 5.12 (d, 7= 10.1 Hz, 1H), 5.10 (d, 7= 9.5 Hz, 1H), 4.61 -4.52 (m, 1H), 4.52-4.44 (m, 1H), 3.91 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.83 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.73 (s, 3H), 3.72 (s, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 1.30 (d, 7= 7.1 Hz, 3H), 1.27 -1.22 (m, 6H), 0.98 (d,7= 7.1 Hz, 3H). 13CNMR(126 MHz, CDCR) for 1:1 mixture of diastereomers δ 172.26, 17E87, 168.91, 162.22, 162.18, 159.42, 159.39, 152.82, 152.77, 152.70, 147.40, 147.32, 147.18, 147.11, 146.63, 141.62, 137.45, 137.41, 135.11, 134.85, 134.76, 134.60, 123.66, 123.64, 121.06, 120.97, 120.48, 120.33, 110.74, 110.61, 110.55, 109.65,73.83,73.78, 60.40, 60.38, 60.31,60.28,56.28, 56.26, 55.65, 55.63, 55.58, 48.01,47.91,41.81,20.76, 18.84, 18.68, 18.48, 18.07.
412
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
496 OS HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2538 1Η NMR (500 MHz, CDCh) for 1:1 mixture of diastereomers δ 8.43 (s, 2H), 8.32 (d, J= 4.4 Hz, 1H), 8.31 (d, 7= 4.4 Hz, 1H), 7.397.30 (m, 2H), 7.13 (t, 7= 9.0 Hz, 2H), 7.05-6.86 (m, 10H), 5.74-5.58 (m,2H), 5.09 (d, 7= 9.7 Hz, 1H), 5.06 (d, 7=9.1 Hz, 1H), 4.53 (dq, 7= 15.5, 7.5 Hz, 2H), 3.91 (s, 3H), 3.90 (s, 3H), 3.83 (s, 3H), 3.79 (s, 3H), 3.70 (s, 3H), 3.68 (s, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 2.30 (s, 3H), 2.29 (s, 3H), 2.25 (s, 6H), 1.30- 1.23 (m, 9H), 0.92 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) for 1:1 mixture of diastereomers δ 172.25, 171.70, 168.90, 162.23, 162.17, 159.44, 159.40, 156.93, 156.89, 156.82, 156.75, 146.64, 146.57, 141.65, 141.59, 137.42, 134.11, 133.96, 133.86, 133.76, 131.20, 131.14, 131.04, 130.95, 130.03, 129.76, 129.70, 126.87, 126.70, 126.65, 126.37, 123.81, 109.65, 74.38, 74.32, 60.31,60.23,60.20,56.29, 56.27, 47.98, 47.84,41.65, 20.75, 19.06, 18.90, 18.41, 18.00, 16.68, 16.47.
413
2019201931 20 Mar 2019
Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
497 X a HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2529 1H NMR (400 MHz, CDC13) for 1:1 mixture of diastereomers δ 8.50 - 8.23 (m, 4H), 7.13-6.92 (m, 8H), 6.86 (t, 7= 7.1 Hz, 2H), 6.73-6.63 (m, 4H), 5.775.58 (m, 2H), 4.61 (t,7=9.4 Hz, 2H), 4.49 (dp, 7= 26.5, 7.1 Hz, 2H), 3.90 (s, 3H), 3.89 (s, 3H), 3.79 (s, 3H), 3.78 (s, 3H), 3.76 (s, 3H), 3.75 (s, 3H), 2.38 (d, 7= 0.9 Hz, 6H), 2.28 (s, 3H), 2.26 (s, 3H), 2.20 (s, 3H),2.18(s, 3H), 1.27 (dt, 7= 6.4, 3.2 Hz, 9H), 0.96 (d, 7 =7.1 Hz, 3H). 13CNMR(101 MHz, CDCI3) for 1:1 mixture of diastereomers δ 172.28, 171.77, 168.85, 162.24, 159.41, 157.72, 157.55, 146.61, 141.63, 140.75, 140.51, 140.12, 137.47, 126.12, 126.08, 125.91, 125.42, 120.51, 120.39, 119.92, 119.76, 109.64, 108.32, 74.77, 74.71, 56.26, 55.45, 53.40, 48.08, 47.90, 47.55,20.72, 18.81, 18.67, 18.29, 17.98, 11.80, 11.73, 11.43.
414
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
498 ex ee (Thin film) 3384, 2942, 1771, 1737, 1677, 1501, 1475, 1430, 1308, 1200, 1175, 1100, 1057, 950, 908, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C29H29F4N2O8, 609.1855; found, 609.1851 3H NMR (400 MHz, CDCfi) 6 8.35 (d, 7= 5.5 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.07 (ddd, 7=8.2, 5.7, 2.2 Hz, 1H), 7.00 (d, 7= 5.5 Hz, 1H), 6.86-6.72 (m, 3H), 5.70-5.62 (m, 1H), 4.85 (d, 7= 9.4 Hz, 1H), 4.62-4.54 (m, 1H), 3.97 (d, 7= 2.3 Hz, 3H),3.91(s, 3H), 3.83 (d,7 = 2.0 Hz, 3H), 2.38 (s, 3H), 1.23 (d, 7=6.1 Hz, 3H), 1.11 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 172.04, 168.90, 162.27, 159.48, 149.41, 147.34- 146.78 (m), 146.60, 143.34, 141.37, 137.50, 129.96- 129.37 (m), 123.61 - 122.42 (m), 110.81 (d,7= 13.5 Hz), 110.68 (d,7= 13.2 Hz), 109.78, 72.31, 61.4460.78 (m), 56.31, 47.89, 42.40, 20.74, 18.77, 18.11.
415
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
499 & (Thin film) 3381,2938, 1771, 1734, 1677, 1504, 1451, 1310, 1198, 1175, 1147, 1043, 908, 806, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O6, 533.2646; found, 533.2651 1H NMR (400 MHz, CDCh) 6 8.43 (s, 1H), 8.32 (d,/ = 5.4 Hz, 1H), 7.11-6.83 (m, 7H), 5.66 (dq,/= 10.0, 6.1 Hz, 1H), 4.57- 4.48 (m, 1H), 4.45 (d,/= 10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.35 (s, 3H), 2.29 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.28 (d,/= 6.2 Hz, 3H), 0.94 (d,/= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.41, 168.91, 162.25, 159.41, 146.64, 141.58, 139.12, 138.59, 137.44, 135.40, 135.07, 133.59, 133.35, 130.56, 130.27, 128.60, 127.91, 127.20, 126.91, 109.68, 74.87, 56.27, 47.90, 47.34, 21.28, 21.22, 20.75, 19.79, 19.73, 18.86, 17.98.
416
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
500 \S- ss (Thin film) 3384, 2938, 1771, 1735, 1677, 1505, 1451, 1309, 1198, 1174, 1100, 1043, 908, 804, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O6, 533.2646; found, 533.2642 1Η NMR (400 MHz, CDCh) 6 8.42 (s, 1H), 8.31 (d,7= 5.5 Hz, 1H), 7.18 (d,7=7.9 Hz, 1H), 7.12 (d, J= 8.6 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.96-6.85 (m, 4H), 5.66 (dq, 7=9.9, 6.2 Hz, 1H), 4.57-4.48 (m, 1H), 4.43 (d, 7= 10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.34 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.28 (d, 7=6.1 Hz, 3H), 0.96 (d, 7= 7.1 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.30, 168.92, 162.24, 159.41, 146.64, 141.59, 137.43, 136.50, 136.40, 136.19, 136.10, 135.84, 135.52, 131.49, 131.15, 127.76, 127.14, 126.81, 126.59, 109.67, 74.83, 56.27, 47.89, 46.82, 20.84, 20.81, 20.76, 20.13, 20.07, 18.92, 18.03.
417
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
501 \y Ss (Thin film) 3379, 2983, 1770, 1738, 1677, 1496, 1453, 1310, 1199, 1176, 1148, 1043, 909, 808, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O6, 541.2145; found, 541.2146 1H NMR (400 MHz, CDCh) 6 8.43 (d, 7= 7.9 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 7.13 -6.98(m, 4H), 6.91 (dd,7= 10.3, 2.8 Hz, 1H), 6.81 (dtd, 7= 12.5, 8.2, 2.7 Hz, 2H), 5.57 (dq, 7=9.6, 6.1Hz, 1H), 4.61-4.51 (m, 1H), 4.46 (d, 7= 9.6 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.34 (s, 3H), 2.29 (s, 3H), 1.32 (d,7 = 6.2 Hz, 3H), 1.02 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.15, 168.90, 162.31, 161.35 (d, 7= 243.7 Hz), 159.42, 146.68, 141.44, 140.63 (d, 7= 6.5 Hz), 140.14 (d, 7= 6.7 Hz), 137.47, 132.40 (d, 7= 3.1 Hz), 132.06 (d, 7= 2.0 Hz), 132.01 (d,7=3.1 Hz), 131.69 (d, 7= 7.8 Hz), 114.83 (d, 7= 22.2 Hz), 114.37 (d, 7= 22.3 Hz), 113.65 (d, 7= 20.8 Hz), 113.37 (d, 7= 20.6 Hz), 109.75, 74.02, 56.28, 47.77, 47.72, 20.75, 19.42, 19.35, 18.83, 18.00.
418
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
502 \S- (Thin film) 3378, 2940, 1770, 1738, 1677, 1498, 1207, 1176, 1151, 1037, 816, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2047 3H NMR (400 MHz, CDC13) 6 8.42 (d, 7= 7.6 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 7.01 -6.97 (m, 1H), 6.96-6.91 (m,2H), 6.88 (d, 7= 9.3 Hz, 1H), 6.86-6.81 (m, 1H), 6.70 (dt, 7= 9.0, 3.5 Hz, 1H), 6.65 (dt, 7= 9.0, 3.5 Hz, 1H), 5.83 (dq, 7= 12.0, 6.1Hz, 1H), 4.69 (d,7= 10.3 Hz, 1H), 4.57 (p, 7= 7.3 Hz, 1H), 3.90 (s, 3H), 3.74 (s, 6H),2.38(s, 3H), 1.30 (d, 7 = 6.2 Hz, 3H), 1.02 (d,7= 7.1Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.11, 168.90, 162.25, 159.42, 155.73 (d, 7 = 1.8 Hz), 155.57 (d, 7= 2.0 Hz), 155.19 (d, 7= 238.6 Hz), 154.96 (d, 7=238.7 Hz), 146.63, 141.51, 137.44, 127.90 (d, 7= 15.8 Hz), 127.66 (d,7= 16.2 Hz), 116.23 (d, 7= 24.8 Hz), 115.96 (d, 7= 24.9 Hz), 115.16, 114.23, 113.21 112.82 (m), 109.69, 72.01, 56.28, 55.71, 47.85, 43.39, 20.75, 18.96, 18.05.
419
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
503 Y- Y (Thin film) 3379, 2938, 1770, 1736, 1676, 1623, 1585, 1506, 1444, 1310, 1195, 1175, 1154, 1031, 907, 832, 803, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2044 1H NMR (400 MHz, CDCfi) 6 8.42 (s, 1H), 8.32 (d,7= 5.4 Hz, 1H), 7.29 (t, 7= 8.7 Hz, 1H), 7.16 (t, 7= 8.5 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.65 - 6.55 (m, 3H), 6.51 (dd,7= 12.0, 2.6 Hz, 1H), 5.78 (dq, 7= 12.1,6.2 Hz, 1H), 4.66- 4.52 (m, 2H), 3.90 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 2.38 (s, 3H), 1.27 (d, 7= 6.2 Hz, 3H), 1.06 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 172.11, 168.91, 162.24, 161.24 (d, 7= 245.7 Hz), 161.01 (d, 7= 245.9 Hz), 159.72 (d,7= 11.2 Hz), 159.46 (d,7= 11.3 Hz), 159.44, 146.60, 141.51, 137.44, 129.90 (d, 7= 5.4 Hz), 129.34 (d, 7= 5.6 Hz), 119.60 (d,7= 14.6 Hz), 119.45 (d,7= 15.0 Hz), 110.13 (d, 7= 3.0 Hz), 109.85- 109.61 (m), 101.99 - 101.44 (m), 72.26, 56.28, 55.50, 55.46, 47.88, 41.64, 20.75, 18.93, 18.13.
420
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
504 & (Thin film) 3381,2942, 1772, 1728, 1679, 1508, 1456, 1417, 1327, 1242, 1172, 1121, 1033, 904, 739 HRMS-ESI (m/z) ([M+H]+) calcd for C31H31F6N2O8, 673.1979; found, 673.1985 3H NMR (400 MHz, CDC13) 6 8.40 (s, 1H), 8.31 (d,7= 5.4 Hz, 1H), 7.54 (d,7=8.0 Hz, 1H), 7.30 (d, J= 7.8 Hz, 1H), 7.12 (d, J= 8.0 Hz, 2H), 7.04 - 6.97 (m, 3H), 6.01-5.91 (m, 1H), 4.99 (d, J= 9.3 Hz, 1H), 4.60-4.46 (m, 1H), 3.90 (s, 3H), 3.89 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 0.98 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.17, 162.27, 159.47, 157.54, 157.39, 146.61, 141.44, 137.49, 132.44, 130.44- 129.46 (m), 117.00, 109.74, 107.51 (d, 7= 25.6 Hz), 99.99, 71.95, 56.28, 55.73, 55.69, 47.82, 43.70, 20.73, 18.89, 17.97.
505 ss OS 3$ (Thin film) 3375, 2939, 1770, 1677, 1592, 1509, 1195, 1136, 1059, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2034 3H NMR (400 MHz, CDCI3) 6 8.42 (d, 7= 7.9 Hz, 1H), 8.32 (d, 7= 5.5 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.666.53 (m, 4H), 6.45 (ddt, 7= 14.8, 10.5, 2.3 Hz, 2H), 5.67 (dq, 7= 9.9, 6.1Hz, 1H), 4.62-4.49 (m, 1H), 3.94 (d, 7= 9.9 Hz, 1H), 3.90 (s, 3H), 3.76 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 1.25 (d,7=7.6 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDC13) δ-110.67, -111.17.
421
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
506 os so OS OS (Thin film) 3375,2938, 1770, 1677, 1593, 1203, 1152, 1064, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O10, 597.2443; found, 597.2442 1H NMR (400 MHz, CDC13) 6 8.42 (d, 7= 7.7 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.45 (dd, 7= 6.5, 2.3 Hz, 4H), 6.28 (dt, 7= 17.4, 2.3 Hz, 2H), 5.74 (dq, 7= 10.3,6.1 Hz, 1H), 4.59-4.48 (m, 1H), 3.93 -3.86 (m, 4H), 3.76 (s, 6H), 3.74 (s, 6H), 2.38 (s, 3H), 1.28- 1.22 (m, 3H), 0.97 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.26, 168.86, 162.29, 160.95, 160.78, 159.43, 146.64, 143.47, 143.25, 141.64, 137.47, 109.69, 106.48, 106.26, 98.54, 98.44, 72.91,58.21, 56.26, 55.30, 55.28, 47.92, 20.73, 19.23, 18.01.
422
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
507 sc CS sc SN (Thin film) 3384, 2939, 1771, 1677, 1593, 1508, 1172, 1152, 1066, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2540 3H NMR (400 MHz, CDC13) 6 8.42 (d, 7= 7.9 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.69 (d, 7= 1.5 Hz, 2H), 6.64 (dt,7= 4.2, 1.9 Hz, 2H), 6.54 (t, 7= 1.9 Hz, 1H), 6.49 (t, 7= 1.9 Hz, 1H), 5.73 (dq, 7= 10.3, 6.1Hz, 1H), 4.59-4.47 (m, 1H), 3.89 (s, 4H), 3.75 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 2.25 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.93 (d, 7= 7.1 Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.30, 168.86, 162.27, 159.77, 159.64, 159.43, 146.64, 142.75, 142.51, 141.67, 139.73, 139.31, 137.46, 121.35, 121.29, 112.68, 111.36, 110.95, 109.68, 73.23, 57.88, 56.26, 55.15, 55.13,47.91, 29.30,21.67,21.60, 20.73, 19.27, 17.96.
423
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
508 SN OS 3$ (Thin film) 3376, 2939, 1771, 1678, 1508, 1201, 1040, 734 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2538 1H NMR (400 MHz, CDC13) 6 8.40 (d,/= 7.9 Hz, 1H), 8.31 (d,/= 5.4 Hz, 1H), 7.06 -6.94(m, 3H), 6.80 (ddd,/ = 7.7,6.1, 1.7 Hz, 2H), 6.73 (dd,/= 14.2, 1.6Hz,2H), 5.79 (dq,/= 10.1,6.1 Hz, 1H), 4.60 - 4.47 (m, 1H), 3.96 (d,/= 10.1 Hz, 1H), 3.89 (s, 3H), 3.79 (s, 3H), 3.79 (s, 3H), 2.38 (s, 3H), 2.14 (s, 3H), 2.11 (s, 3H), 1.24 (d,/= 6.4 Hz, 3H), 0.93 (d, /= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.31, 168.86, 162.28, 159.44, 157.84, 157.65, 146.62, 141.65, 140.39, 140.28, 137.48, 130.75, 130.48, 125.19, 124.79, 119.76, 119.68, 109.94, 109.85, 109.69, 73.32, 57.89, 56.26, 55.29, 47.93,29.30, 20.73, 19.30, 17.97, 15.80, 15.75.
424
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
509 Y >'V (Thin film) 3373, 2939, 1770, 1676, 1513, 1276, 1201, 1026, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O8, 573.2043; found, 573.2033 1H NMR (400 MHz, CDCh) 6 8.40 (d, 7= 7.9 Hz, 1H), 8.32 (d, 7= 5.4 Hz, 1H), 7.04 -6.91 (m, 5H), 6.86 (dt,7= 11.1, 8.7 Hz, 2H), 5.63 (dq,7 = 9.4, 6.1Hz, 1H), 4.644.51 (m, 1H), 3.92 (d, 7= 9.5 Hz, 1H), 3.90 (s, 3H), 3.84 (s, 3H), 3.82 (s, 3H),2.38(s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 1.05 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCh) δ-134.20, -134.64.
510 A Y A (Thin film) 3386, 2939, 1771, 1677, 1504, 1201, 1176, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2526 1H NMR (400 MHz, CDCh) 6 8.43 (s, 1H), 8.31 (d,7= 5.5 Hz, 1H), 7.12-6.94 (m, 5H), 6.70 (dd, 7= 14.1, 8.4 Hz,2H), 5.69 (dq, 7=9.9, 6.1Hz, 1H), 4.60-4.49 (m, 1H), 3.89 (s, 3H), 3.87 (d,7 = 10.6 Hz, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.38 (s, 3H), 2.16 (s, 3H), 2.14 (s, 3H), 1.21 (d,7=6.1 Hz, 3H), 0.95 (d, 7= 7.1 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.30, 168.86, 162.26, 159.43, 156.52, 156.35, 146.63, 141.69, 137.46, 133.70, 133.57, 130.50, 130.37, 126.79, 126.37, 126.10, 125.87, 110.05, 109.92, 109.67, 73.70, 56.26, 56.23, 55.31, 55.29, 47.94, 20.73, 19.29, 18.08, 16.32, 16.25.
425
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
511 AN AS (Thin film) 3387, 2940, 1771, 1678, 1499, 1223, 1046, 808, 732 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O10, 597.2443; found, 597.2410 1H NMR (400 MHz, CDCR) 6 8.50-8.35 (m, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.07 (d, 7= 3.0 Hz, 1H), 6.97 (d,7= 5.5 Hz, 1H), 6.87 (d,7=3.0 Hz, 1H), 6.80-6.60 (m, 4H), 5.91 (dq, 7= 9.9, 6.1 Hz, 1H), 4.93 (d,7= 10.0 Hz, 1H), 4.62 - 4.45 (m, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 3.70 (s, 3H), 2.38 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.97 (d, 7= 7.1 Hz, 3H). 13CNMR(101 MHz, CDCR) δ 172.29, 168.87, 162.24, 159.40, 153.47, 153.45, 151.89, 151.77, 146.63, 141.73, 137.43, 130.69, 116.44, 115.43, 112.14, 112.11, 111.84, 111.55, 109.63, 73.04, 56.33, 56.29, 56.25, 55.68, 55.59, 47.96, 43.90, 29.30, 20.73, 18.91, 18.13.
426
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
512 QR QS A A (Thin film) 3381,2939, 1771, 1677, 1502, 1200, 1175, 1043, 731 HRMS-ESI (m/z) ([M+H]+) calcd for C31H37N2O8, 565.2544; found, 565.2543 1H NMR (400 MHz, CDCfi) 6 8.43 (d, 7= 8.0 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.05 (d, 7= 8.3 Hz, 1H), 7.016.94 (m,2H), 6.90 (d,7=2.7 Hz, 1H), 6.82 (d, 7= 2.7 Hz, 1H), 6.63 (ddd, 7= 18.7, 8.4, 2.7 Hz, 2H), 5.65 (dq,7= 10.1, 6.1Hz, 1H), 4.594.49 (m, 1H), 4.45 (d,7= 10.0 Hz, 1H), 3.89 (s, 3H), 3.73 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.27 (s, 3H), 1.31 (d,7=6.1 Hz, 3H), 0.97 (d, 7= 7.1 Hz, 3H). 13CNMR(101 MHz, CDCfi) δ 172.26, 168.85, 162.28, 159.43, 157.92, 157.89, 146.64, 141.63, 140.31, 139.86, 137.47, 131.43, 131.10, 128.88, 128.61, 114.65, 113.69, 111.27, 111.11, 109.70, 74.59, 56.26, 55.19, 47.90, 47.86, 29.30, 20.73, 19.29, 19.25, 18.90, 17.99.
427
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
513 ss AS (Thin film) 3381,2940, 1740, 1675, 1592, 1505, 1200, 1134, 1045, 829, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O9, 603.2149; found, 603.2137 A NMR (400 MHz, CDCh) 6 8.27 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 6.94 (d,7=5.4 Hz, 1H), 6.60 (dddd, 7= 13.2, 10.8,3.9, 1.8 Hz, 4H), 6.45 (ddt, 7= 13.9, 10.5, 2.3 Hz, 2H), 5.76 -5.63 (m, 3H), 4.57 (p, 7= 7.3 Hz, 1H), 3.95 (d, 7= 10.0 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 2.06 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCh) 6-110.67, -111.20.
514 Ύ CS A (Thin film) 3382, 2937, 1737, 1675, 1593, 1457, 1202, 1150, 1062, 829, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O11, 627.2548; found, 627.2555 A NMR (400 MHz, CDCh) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 6.93 (d, 7= 5.4 Hz, 1H), 6.46 (dd, 7=7.4, 2.2 Hz, 4H), 6.28 (dt, 7= 16.6, 2.2 Hz, 2H), 5.81-5.68 (m, 3H), 4.55 (p, 7= 7.2 Hz, 1H), 3.96-3.86 (m, 4H), 3.76 (s, 6H), 3.74 (s, 6H), 2.06 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 0.99 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) 6 172.37, 170.22, 162.89, 160.96, 160.79, 160.25, 145.70, 143.93, 143.51, 143.26, 142.65, 109.51, 106.49, 106.24, 98.54, 98.43, 89.57, 72.87, 58.24, 56.17, 55.30, 55.28, 48.14, 20.85, 19.25, 17.84.
428
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
515 SN (Thin film) 3382, 2937, 1738, 1676, 1594, 1504, 1293, 1202, 1152 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O9, 595.2650; found, 595.2647 3H NMR (400 MHz, CDC13) 6 8.27 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 6.93 (d, 7= 5.4 Hz, 1H), 6.70 (s, 2H), 6.65 (dt, 7=5.7, 1.9 Hz, 2H), 6.55 (t, 7= 1.7 Hz, 1H), 6.50 (t, 7= 1.7 Hz, 1H), 5.80-5.66 (m, 3H), 4.54 (p, 7= 7.2 Hz, 1H), 3.93-3.87 (m,4H), 3.75 (d, 7= 7.3 Hz, 6H), 2.29 (s, 3H), 2.25 (s, 3H), 2.06 (s, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 0.95 (d,7= 7.1Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.41, 170.22, 162.88, 160.25, 159.77, 159.65, 145.70, 143.93, 142.79, 142.70, 142.52, 139.73, 139.31, 121.35, 121.30, 112.69, 111.36, 110.92, 109.50, 89.57, 73.19, 57.91, 56.16, 55.15, 55.14, 48.13,29.30,21.67,21.60, 20.85, 19.29, 17.79.
429
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
516 (Thin film) 3382, 2936, 1737, 1676, 1505, 1202, 1040, 969, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O9, 595.2650; found, 595.2639 1H NMR (400 MHz, CDC13) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.21 (d, 7= 7.8 Hz, 1H), 7.05 -6.96 (m, 2H), 6.93 (d,7= 5.4 Hz, 1H), 6.81 (td,7= 7.4, 1.6 Hz, 2H), 6.76 (d,7 = 1.6 Hz, 1H), 6.72 (d,7= 1.6 Hz, 1H), 5.79 (dq, 7 = 10.1, 6.2 Hz, 1H), 5.72 (d,7= 1.4 Hz, 2H), 4.55 (p, 7= 7.2 Hz, 1H), 3.97 (d, 7= 10.2 Hz, 1H), 3.90 (s, 3H), 3.80 (s, 3H), 3.79 (s, 3H), 2.14 (s, 3H), 2.11 (s, 3H), 2.06 (s, 3H), 1.26 (d, 7= 6.2 Hz, 3H), 0.94 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCI3) δ 172.43, 170.21, 162.89, 160.26, 157.85, 157.65, 145.68, 143.94, 142.67, 140.44, 140.28, 130.75, 130.48, 125.19, 124.78, 119.75, 119.67, 109.94, 109.86, 109.52, 89.56, 73.28,57.91,56.17, 55.29, 55.28, 48.16, 20.85, 19.32, 17.82, 15.80, 15.75.
430
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
517 Ύ A (Thin film) 3382, 2984, 1739, 1675, 1512, 1275, 1202, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C30H33F2N2O9, 603.2149; found, 603.2137 XH NMR (400 MHz, CDCh) 6 8.27 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.9 Hz, 1H), 7.04 -6.92 (m, 5H), 6.87 (q,7= 8.7 Hz, 2H), 5.72 (s, 2H), 5.64 (dq, 7=9.5, 6.2 Hz, 1H), 4.65 - 4.48 (m, 1H), 3.93 (d, 7= 9.7 Hz, 1H), 3.91 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 2.06 (s, 3H), 1.24 (d,7 = 6.1 Hz, 3H), 1.06 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-134.20, -134.65.
518 (Thin film) 3382, 2941, 1737, 1676, 1503, 1248, 1203, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O9, 595.2650; found, 595.2645 1H NMR (400 MHz, CDCh) 6 8.27 (s, 1H), 8.23 (d,7= 7.9 Hz, 1H), 7.11 -6.99 (m, 5H), 6.93 (d, 7= 5.3 Hz, 1H), 6.71 (dd,7= 12.0, 8.4 Hz, 2H), 5.74 - 5.65 (m, 3H), 4.55 (p, 7= 7.2 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 2.16 (s, 3H), 2.14 (s, 3H), 2.06 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.43, 170.22, 162.87, 160.26, 156.53, 156.36, 145.68, 143.94, 142.72, 133.75, 133.58, 130.48, 130.36, 126.81, 126.38, 126.10, 125.87, 110.06, 109.93, 109.49, 89.58, 73.66,56.27,56.16, 55.33, 55.30, 48.16, 20.85, 19.32, 17.91, 16.33, 16.25.
431
2019201931 20 Mar 2019
Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
519 •A <2S5 (Thin film) 3381,2939, 1737, 1676, 1498, 1233, 1043, 729 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O11, 627.2548; found, 627.2541 1H NMR (400 MHz, CDC13) 6 8.25 (dd, J= 6.5, 3.4 Hz, 2H), 7.07 (d, 7= 3.0 Hz, 1H), 6.92 (d, 7= 5.4 Hz, 1H), 6.87 (d, 7= 3.1 Hz, 1H), 6.77 (d, 7= 8.8 Hz, 1H), 6.71 (d, 7= 8.8 Hz, 1H), 6.66 (ddd, 7= 11.1, 8.9, 3.0 Hz, 2H), 5.92 (dq,7 = 9.9, 6.1 Hz, 1H), 5.72 (d,7 = 1.7 Hz, 2H), 4.94 (d,7= 10.0 Hz, 1H), 4.56 (p, 7= 7.2 Hz, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 3.72 (s, 3H), 3.71 (s, 3H), 2.06 (s, 3H), 1.25 (d, 7= 6.3 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCh) δ 172.39, 170.22, 162.84, 160.23, 153.47, 153.45, 151.89, 151.78, 145.68, 143.88, 142.78, 130.73, 130.69, 116.45, 115.38, 112.14, 112.13, 111.83, 111.55, 109.45, 89.59, 73.02, 56.34, 56.29, 56.15, 55.67, 55.59, 48.17, 43.90, 20.86, 18.91, 17.97.
432
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
520 (Thin film) 3382, 2937, 1739, 1677, 1500, 1455, 1202, 1042, 730 HRMS-ESI (m/z) ([M+H]+) calcd for C32H39N2O9, 595.2650; found, 595.2652 3H NMR (400 MHz, CDCfi) 6 8.26 (d, 7= 5.4 Hz, 1H), 8.23 (d, 7= 7.8 Hz, 1H), 7.05 (d, 7= 8.5 Hz, 1H), 6.98 (d, 7= 8.4 Hz, 1H), 6.93 (d,7= 5.4 Hz, 1H), 6.90 (d,7=2.7 Hz, 1H), 6.82 (d, 7= 2.7 Hz, 1H), 6.63 (ddd, 7= 18.1, 8.3, 2.7 Hz, 2H), 5.72 (d,7= 1.6 Hz, 2H), 5.66 (dq, 7 = 10.0, 6.1Hz, 1H), 4.56 (p, 7= 7.3 Hz, 1H), 4.46 (d, 7= 10.1 Hz, 1H), 3.90 (s, 3H), 3.73 (s, 6H), 2.33 (s, 3H), 2.28 (s, 3H), 2.06 (s, 3H), 1.32 (d,7 = 6.1 Hz, 3H), 0.99 (d,7= 7.2 Hz, 3H). 13CNMR(101 MHz, CDCfi) δ 172.37, 170.22, 162.89, 160.25, 157.92, 157.89, 145.69, 143.92, 142.66, 140.37, 139.85, 131.44, 131.11, 128.89, 128.62, 114.67, 113.64, 111.28, 111.11, 109.52, 89.57, 74.55,56.17,55.19, 48.13,47.87, 29.30, 20.86, 19.30, 19.26, 18.88, 17.81.
433
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
521 ¥ X X ¥ (Thin film) 3380, 2933, 1769, 1737, 1677, 1496, 1195, 1174, 1095 HRMS-ESI (m/z) ([M+H]+) calcd for C31H35F2N2O8, 602.2389; found, 602.2395 1H NMR (400 MHz, CDC13) δ 8.39 (d, J= 7.1 Hz, 1H), 8.31 (d,/= 5.4 Hz, 1H), 7.44 (dd,/=8.7, 5.6 Hz, 1H), 7.23 (dd,/=8.7, 5.6 Hz, 1H), 7.11 (dd,/= 9.6, 2.8 Hz, 1H), 7.07 (dd,/=9.7, 2.8 Hz, 1H), 7.00 (d,/= 5.5 Hz, 1H), 6.96-6.87 (m, 2H), 5.60 (dq,/= 8.5, 6.2 Hz, 1H), 4.69 (d,/= 8.8 Hz, 1H), 4.62 (d,/= 12.4 Hz, 1H), 4.60-4.53 (m, 1H), 4.50 (d,/= 12.6 Hz, 1H), 4.44 (d,/= 12.5 Hz, 1H), 4.40 (d,/= 12.5 Hz, 1H), 3.90 (s, 3H), 3.43 (s, 3H), 3.38 (s, 3H), 2.39 (s, 3H), 1.28 (d,/= 6.2 Hz, 3H), 1.04 (d, /= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-115.57, -115.90.
434
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
522 Y Y ss > (Thin film) 3385, 2976, 1770, 1738, 1678, 1506, 1200, 1175, 1155,1096 HRMS-ESI (m/z) ([M+H]+) calcd for C33H39F2N2O8, 629.2669; found, 629.2666 1H NMR (400 MHz, CDCh) 6 8.40 (d, 7= 6.4 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.45 (dd, 7=8.7, 5.6 Hz, 1H), 7.21 (dd, 7=8.7, 5.6 Hz, 1H), 7.17-7.05 (m, 2H), 7.00 (d, 7= 5.5 Hz, 1H), 6.97 -6.82(m, 2H), 5.62 (dq,7 = 8.2, 6.2 Hz, 1H), 4.70 (d,7 = 8.7 Hz, 1H), 4.67 (d,7= 12.7 Hz, 1H), 4.62-4.50 (m, 2H), 4.48 (d, 7= 12.5 Hz, 1H), 4.43 (d, 7= 12.7 Hz, 1H), 3.90 (s, 3H), 3.623.45 (m, 4H), 2.39 (s, 3H), 1.30- 1.25 (m, 6H), 1.23 (t, 7= 7.0 Hz, 3H), 1.05 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-115.69, -115.98.
523 HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O7, 525.2037; found, 525.2025 1H NMR (400 MHz, CDCh) 6 8.41 (d, 7= 6.8 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.36 -7.28(m, 2H), 7.26-7.18 (m, 2H), 7.18-7.10 (m, 2H), 6.97 (d, 7= 5.5 Hz, 1H), 6.67 -6.46(m,2H), 5.83 (dq,7 = 9.9, 6.2 Hz, 1H), 4.62 - 4.46 (m,2H), 3.87 (s, 3H), 3.82 (s, 3H), 2.38 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 0.91 (d,7= 7.1Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.24.
435
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
524 \S- HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O6, 509.2088; found, 509.2083 1H NMR (400 MHz, CDCh) 6 8.40 (d, 7= 7.9 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.35 -7.17(m, 5H), 7.17-7.08 (m, 1H), 6.97 (d, 7= 5.5 Hz, 1H), 6.93 - 6.79 (m, 2H), 5.77 (dq, 7= 10.2,6.1 Hz, 1H), 4.60 - 4.47 (m, 1H), 4.28 (d, 7= 10.2 Hz, 1H), 3.87 (s, 3H), 2.38 (s,6H), 1.26 (d, 7= 6.1 Hz, 3H), 0.93 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-116.66.
525 \S- A HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O7, 525.2037; found, 525.2035 1H NMR (400 MHz, CDCh) 6 8.42 (d, 7= 8.1 Hz, 1H), 8.30 (d, 7= 5.6 Hz, 1H), 7.35 -7.21(m, 5H), 7.17 (ddt, 7= 6.5,5.4, 1.8 Hz, 1H), 6.98 (d, 7= 5.4 Hz, 1H), 6.58 (td, 7= 8.3, 2.6 Hz, 1H), 6.51 (dd,7 = 10.9, 2.5 Hz, 1H), 5.81 (dq,7= 10.1, 6.1Hz, 1H), 4.63 -4.43 (m, 2H), 3.87 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 2.15 (s, 3H),, 0.99 (d, 7 = 7.1 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.59.
436
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
526 X OS HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O6, 509.2088; found, 509.2079 1H NMR (400 MHz, CDCh) δ 8.47 - 8.36 (m, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.35 (dd, 7=8.7, 5.7 Hz, 1H), 7.307.15 (m, 5H), 6.99 (d,7=5.5 Hz, 1H), 6.85 (td, 7= 8.4, 2.8 Hz, 1H), 6.79 (dd,7 = 9.8, 2.8 Hz, 1H), 5.73 (dq,7 = 10.0, 6.1 Hz, 1H), 4.604.47 (m, 1H), 4.26 (d,7= 10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.30 (s, 3H), 1.23 (d, 7=6.1 Hz, 3H), 0.96 (d, 7= 7.1 Hz, 3H). 19F NMR (376 MHz, CDCh) δ -117.14.
527 so as HRMS-ESI (m/z) ([M+H]+) calcd for C29H32FN2O7, 539.2193; found, 539.2180 1H NMR (400 MHz, CDCh) 6 8.41 (d, 7= 5.0 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.23 -7.19(m, 2H), 7.19-7.10 (m, 1H), 7.03 (d, 7= 7.9 Hz, 2H), 6.97 (d, 7= 5.5 Hz, 1H), 6.63 - 6.50 (m, 2H), 5.80 (dq, 7=9.6, 6.1Hz, 1H), 4.61 -4.46 (m, 2H), 3.88 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 0.95 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) 6-113.44.
437
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
528 sc sc CN CN HRMS-ESI (m/z) ([M+H]+) calcd for C29H32FN2O6, 523.2244; found, 523.2235 3H NMR (400 MHz, CDCh) 6 8.40 (d, 7= 8.6 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.28 (dd,7=8.8, 5.9 Hz, 1H), 7.18 - 7.10 (m,2H), 7.02 (d, 7= 7.9 Hz, 2H), 6.98 (d,7= 5.5 Hz, 1H), 6.92 - 6.78 (m, 2H), 5.74 (dq, 7=10.0, 6.1 Hz, 1H), 4.62 - 4.45 (m, 1H), 4.24 (d,7= 10.1 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 2.37 (s, 3H), 2.24 (s, 3H), 1.24 (d, 7= 6.1 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-116.88.
529 SC HRMS-ESI (m/z) ([M+H]+) calcd for C29H32FN2O7, 539.2193; found, 539.2182 3H NMR (400 MHz, CDCI3) 6 8.41 (d, 7= 7.9 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.37 -7.23(m, 1H), 7.20-7.12 (m,2H), 7.06 (d, 7= 7.8 Hz, 2H), 6.98 (d, 7= 5.5 Hz, 1H), 6.57 (td, 7= 8.3, 2.5 Hz, 1H), 6.50 (dd,7=11.0, 2.6 Hz, 1H), 5.78 (dq,7= 10.2, 6.1Hz, 1H), 4.69-4.41 (m,2H), 3.89 (s, 3H), 3.76 (s, 3H), 2.38 (s, 3H), 2.27 (s, 3H), 1.21 (d, 7= 6.1 Hz, 3H), 0.98 (d, 7= 7.1 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.82.
438
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
530 aa as SA HRMS-ESI (m/z) ([M+H]+) calcd for C29H32FN2O6, 523.2244; found, 523.2229 1H NMR (400 MHz, CDCh) 6 8.40 (s, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.33 (dd,7= 8.7, 5.8 Hz, 1H), 7.20 - 7.04 (m,4H), 6.98 (d, 7= 5.5 Hz, 1H), 6.84 (td, 7= 8.5, 2.9 Hz, 1H), 6.77 (dd,7=9.6, 2.4 Hz, 1H), 5.71 (dq,7= 10.1, 6.1Hz, 1H), 4.61-4.45 (m, 1H), 4.21 (d,7= 10.1 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.30 (s, 3H), 2.28 (s, 3H), 1.23 (d, 7= 6.0 Hz, 3H), 0.96 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-117.33.
531 A HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1943; found, 543.1936 1H NMR (400 MHz, CDCh) 6 8.40 (d, 7= 6.0 Hz, 1H), 8.30 (d, 7= 5.5 Hz, 1H), 7.35 -7.22(m,2H), 7.13 (dd,7= 8.3, 6.4 Hz, 1H), 6.99 (d,7= 5.5 Hz, 1H), 6.96 - 6.84 (m, 2H), 6.65 - 6.51 (m, 2H), 5.79 (dq, 7=9.7, 6.2 Hz, 1H), 4.64 - 4.47 (m, 2H), 3.88 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 1.23 (d,7=6.1 Hz, 3H), 0.99 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-112.92, -116.48.
439
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
532 HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O6, 527.1993; found, 527.1984 1H NMR (400 MHz, CDCfi) δ 8.39 (d, J= 8.2 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.29 -7.19(m, 3H), 6.99 (d,7= 5.5 Hz, 1H), 6.94-6.81 (m, 4H), 5.71 (dq, 7= 10.1,6.1 Hz, 1H), 4.60 - 4.49 (m, 1H), 4.26 (d,7= 10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.35 (s, 3H), 1.25 (d,7=6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ-116.02, -116.38.
533 HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O7, 543.1943; found, 543.1928 1H NMR (400 MHz, CDCfi) 6 8.41 (d, 7= 5.8 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.33 -7.18(m, 3H), 7.02-6.89 (m, 3H), 6.58 (td, 7= 8.4, 2.5 Hz, 1H), 6.52 (dd,7=10.9, 2.6 Hz, 1H), 5.76 (dq,7= 10.0, 6.2 Hz, 1H), 4.60-4.46 (m, 2H), 3.88 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 1.21 (d, 7= 6.2 Hz, 3H), 1.01 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) δ-113.26, -116.11.
440
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
534 S' RS SR SR HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O6, 527.1993; found, 527.1985 1H NMR (400 MHz, CDCfi) 6 8.40 (d, 7= 8.1 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.33 (dd,7=8.6, 5.7 Hz, 1H), 7.23-7.13 (m,2H), 7.046.92 (m, 3H), 6.86 (td, 7= 8.5, 2.8 Hz, 1H), 6.80 (dd,7 = 9.7, 2.8 Hz, 1H), 5.69 (dq, 7=9.9, 6.2 Hz, 1H), 4.634.45 (m, 1H), 4.24 (d,7=9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.99 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCfi) 6-115.54, -116.80.
535 SR 'R' SR A (Thin film) 3385, 2982, 1771, 1737, 1679, 1605, 1508 HRMS-ESI (m/z) ([M+H]+) calcd for C29H33N2O6, 505.233; found, 505.2333 1H NMR (400 MHz, CDCfi) δ 8.49-8.39 (m, 1H), 8.30 (d, 7= 5.5 Hz, 1H), 7.197.05 (m,6H), 7.01-6.92 (m, 3H), 5.78 (dq, 7=10.2, 6.1 Hz, 1H), 4.59- 4.46 (m, 1H), 3.96 (d, 7= 10.2 Hz, 1H), 3.86 (s, 3H), 2.37 (s, 3H), 2.30 (s, 3H), 2.27 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H).
441
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
536 \S- A A (Thin film) 3377, 2985, 1771, 1736, 1677, 1502, 1195 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O7, 557.2094; found, 557.2082 3H NMR (400 MHz, CDC13) 6 8.41 (d, 7= 5.6 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.23 (dd, 7= 8.5, 6.6 Hz, 1H), 7.16 (dd, 7= 8.6, 5.9 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.81 (qd, 7= 9.1, 8.3, 2.8 Hz, 2H), 6.57 (td, 7= 8.3, 2.5 Hz, 1H), 6.51 (dd,7 = 10.8, 2.5 Hz, 1H), 5.68 (dq,7= 10.0, 6.1Hz, 1H), 4.74 (d,7= 10.0 Hz, 1H), 4.62-4.49 (m, 1H), 3.90 (s, 3H), 3.76 (s, 3H), 2.42 (s, 3H),2.38(s, 3H), 1.21 (d,7 = 5.9 Hz, 3H), 1.04 (d,7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-113.52, -117.02.
537 A vS sn SN (Thin film) 3376, 2940, 1770, 1737, 1678, 1601, 1502, 1196 HRMS-ESI (m/z) ([M+H]+) calcd for C28H28F3N2O7, 561.1843; found, 561.1836 1H NMR (400 MHz, CDCI3) 6 8.40 (d, 7= 6.1 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.31 (dd, 7= 8.4, 6.7 Hz, 1H), 7.23-7.14 (m, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.84-6.68 (m,2H), 6.58 (td, 7= 8.3, 2.5 Hz, 1H), 6.52 (dd,7=10.8, 2.5 Hz, 1H), 5.86-5.73 (m, 1H), 4.78 (d, 7= 9.9 Hz, 1H), 4.65 - 4.43 (m, 1H), 3.90 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 1.24 (d,7=6.1 Hz, 3H), 1.04 (d, 7= 7.2 Hz, 3H).
442
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
538 A X (Thin film) 3378, 2986, 1770, 1736, 1677, 1501, 1196 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O7, 557.2094; found, 557.2091 3H NMR (400 MHz, CDCh) δ 8.44-8.37 (m, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.33 (dd, 7=8.5, 5.8 Hz, 1H), 7.04 (dd, 7= 8.4, 6.8 Hz, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.88 -6.74 (m, 2H), 6.64-6.53 (m, 2H), 5.67 (dq,7=9.8, 6.1Hz, 1H), 4.74 (d,7=9.8 Hz, 1H), 4.62 - 4.45 (m, 1H), 3.90 (s, 3H), 3.84 (s, 3H), 2.38 (s, 3H), 2.27 (s, 3H), 1.25 (d, 7= 6.2 Hz, 3H), 0.98 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDCh) δ-112.97, -117.43.
539 SN Y V (Thin film) 3377, 2983, 1771, 1738, 1677, 1502, 1201 HRMS-ESI (m/z) ([M+H]+) calcd for C28H28F3N2O6, 545.1894; found, 545.1896 1H NMR (400 MHz, CDCh) δ 8.43 -8.35 (m, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.33 (dd, 7=8.6, 5.7 Hz, 1H), 7.197.07 (m, 1H), 7.00 (d,7=5.5 Hz, 1H), 6.90 - 6.74 (m, 4H), 5.68 (dq, 7=12.0, 6.1 Hz, 1H), 4.62 (d, 7= 9.9 Hz, 1H), 4.61-4.49 (m, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.27 (d,7=6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H).
443
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
540 X NA X (Thin film) 3388, 2985, 1771, 1737, 1679, 1572, 1508, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O6, 509.2082; found, 509.2078 'Η NMR (300 MHz, CDCR) 6 8.43 (d, 7= 8.0 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.37 -7.21 (m, 5H), 7.24-7.14 (m, 1H), 6.98 (d, 7= 5.5 Hz, 1H), 6.89-6.84 (m, 1H), 6.79-6.72 (m, 1H), 5.905.72 (m, 1H), 4.56 (dq,7= 8.1,7.1Hz, 1H), 4.41 (d,7= 10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H), 1.24 (d, 7= 6.2 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H).
541 k (Thin film) 3378, 2984, 1771, 1737, 1679, 1509 HRMS-ESI (m/z) ([M+H]+) calcd for C28H29F2N2O6, 527.1988; found, 527.1975 1H NMR (400 MHz, CDCR) 6 8.42 (d, 7= 8.2 Hz, 1H), 8.31 (dd,7=5.5, 1.2 Hz, 1H), 7.29-7.17 (m, 3H), 7.07-6.89 (m, 3H), 6.87 (dd,7=8.0, 1.7 Hz, 1H), 6.80-6.72 (m, 1H), 5.75 (dq, 7= 9.7, 6.1Hz, 1H), 4.62-4.50 (m, 1H), 4.39 (d, 7= 9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.26-1.21 (m, 3H), 1.01 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCR) δ-115.67, -118.89.
444
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
542 Ss 'S NS Y Y (Thin film) 3390, 2984, 1772, 1737, 1678, 1508, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C29H32FN2O6, 523.2239; found, 523.2241 1H NMR (400 MHz, CDC13) δ 8.48 - 8.36 (m, 1H), 8.29 (d,/= 5.6 Hz, 1H), 7.267.21 (m, 1H), 7.20-7.16 (m, 2H), 7.07 (d,/= 7.9 Hz, 2H), 6.96 (d,/= 5.5 Hz, 1H), 6.84 (dd,/=8.1,1.9 Hz, 1H), 6.74 (dd,/= 11.3, 2.2 Hz, 1H), 5.83 -5.73 (m, 1H), 4.63-4.50 (m, 1H), 4.37 (d,/= 10.1 Hz, 1H), 3.86 (s, 3H), 2.37 (s, 3H), 2.27 (s, 3H), 2.22 (s, 3H), 1.24 (d,/= 6.1 Hz, 3H), 1.00 (d, /= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-119.02.
543 Y A (Thin film) 3384, 2983, 1772, 1737, 1679, 1591, 1507, 1452 HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O6, 541.2145; found, 541.2138 1H NMR (400 MHz, CDCI3) 6 8.42 (d,/= 7.9 Hz, 1H), 8.31 (d,/= 5.4 Hz, 1H), 7.24 (dd,/=9.6, 5.7 Hz, 1H), 7.17 (t,/= 7.9 Hz, 1H), 6.99 (d,/= 5.5 Hz, 1H), 6.886.82 (m, 3H), 6.75 (dd,/= 11.3,2.2 Hz, 1H), 5.72 (dq,/ = 9.8, 6.1Hz, 1H), 4.63 (d, J = 10.0 Hz, 1H), 4.62-4.51 (m, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H), 1.26 (d,/= 6.1 Hz, 3H), 1.05 (d,/= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCI3) δ-116.51, -118.10.
445
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
544 ss v\'\ SN (Thin film) 3381,2984, 1771, 1739, 1678, 1504, 1453, 1432 HRMS-ESI (m/z) ([M+H]+) calcd for C28H28F3N2O6; 545.1894; found, 545.1885 3H NMR (400 MHz, CDC13) δ 8.45 - 8.39 (m, 1H), 8.31 (d, 7= 5.5 Hz, 1H), 7.327.20 (m,2H), 6.99 (d,7=5.5 Hz, 1H), 6.88-6.84 (m, 1H), 6.84-6.73 (m, 3H), 5.85-5.74 (m, 1H), 4.70 (d, 7= 9.9 Hz, 1H), 4.63-4.52 (m, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.27 (d, 7= 6.1 Hz, 3H), 1.04 (d,7= 7.2 Hz, 3H).
545 S' ¥ Y (Thin film) 3378, 2982, 1770, 1734, 1675, 1508, 1451, 1309, 1200, 1174, 1046, 907, 802, 730, 699 ESIMS m/z 491.2 ([M+H]+) 3H NMR (500 MHz, CDCI3) δ 8.41 (s, 1H), 8.32 (d,7 = 5.5 Hz, 1H), 7.31 -7.27 (m, 2H), 7.22 (t, 7= 7.7 Hz, 2H), 7.17 (d, 7= 8.1 Hz, 2H), 7.15 -7.10(m, 1H), 7.09 (d,7= 7.9 Hz, 2H), 6.99 (d,7=5.5 Hz, 1H), 5.79 (dq, 7 = 10.1, 6.1Hz, 1H), 4.57-4.47 (m, 1H), 4.01 (d, 7= 10.1 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.24 (d,7 = 6.2 Hz, 3H), 0.88 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.24, 168.91, 162.24, 159.40, 146.64, 141.73, 141.57, 138.27, 137.43, 136.47, 129.44, 128.46, 127.99, 126.56, 109.68, 73.36, 57.53, 56.27, 47.83, 20.97, 20.75, 19.24, 17.92.
446
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
546 ex k (Thin film) 3381,2982, 1770, 1734, 1675, 1507, 1435, 1309, 1199, 1174, 1045, 907, 804, 729, 699 ESIMS m/z 491.2 ([M+H]+) 3H NMR (500 MHz, CDCfi) 6 8.42 (s, 1H), 8.32 (d,7= 5.4 Hz, 1H), 7.29-7.23 (m, 4H), 7.18 (td, 7= 6.0, 2.8 Hz, 3H), 7.04 (d, 7= 7.9 Hz, 2H), 6.99 (d, 7= 5.5 Hz, 1H), 5.79 (dq, 7= 9.8, 6.2 Hz, 1H), 4.57-4.49 (m, 1H), 4.02 (d, 7= 9.9 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.23 (d,7 = 6.2 Hz, 3H), 0.93 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCfi) δ 172.23, 168.92, 162.25, 159.41, 146.64, 141.59, 138.34, 137.44, 136.15, 129.13, 128.72, 128.09, 127.99, 126.77, 109.68, 73.38, 57.41, 56.28, 47.87, 20.94, 20.76, 19.25, 18.00.
447
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
547 •$\ A A (Thin film) 3380, 2982, 1770, 1735, 1676, 1507, 1451, 1310, 1200, 1175, 1158, 1047, 908, 816, 769, 729 ESIMS m/z 509.1 ([M+H]+) 1H NMR (500 MHz, CDCI3) 6 8.41 (s, 1H), 8.32 (d,7= 5.4 Hz, 1H), 7.23 (dd,7 = 8.7, 5.3 Hz, 2H), 7.18-7.13 (m,2H), 7.05 (d, 7= 7.8 Hz, 2H), 7.01 - 6.93 (m, 3H), 5.74 (dq, 7=9.6, 6.2 Hz, 1H), 4.58-4.50 (m, 1H), 4.01 (d, 7= 9.6 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.26 (s, 3H), 1.22 (d, 7= 6.2 Hz, 3H), 0.94 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCI3) δ 172.18, 168.91, 162.26, 161.64 (d, 7= 245.3 Hz), 159.43, 146.63, 141.54, 138.05, 137.45, 137.32 (d, 7= 3.3 Hz), 136.34, 129.56 (d, 7= 7.8 Hz), 129.22, 127.94, 115.53 (d, 7= 21.3 Hz), 109.70, 73.21, 56.51, 56.28, 47.85, 20.94, 20.75, 19.15, 17.99.
448
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (A, 13c, 19f)
548 is Sx A A (Thin film) 3379, 2983, 1770, 1736, 1676, 1509, 1452, 1310, 1201, 1175, 1046, 908, 817, 732, 700 ESIMS m/z 495.1 ([M+H]+) A NMR (500 MHz, CDCh) 6 8.40 (s, 1H), 8.32 (d,7= 5.4 Hz, 1H), 7.33-7.23 (m, 6H), 7.23-7.17 (m, 1H), 6.99 (d, J= 5.5 Hz, 1H), 6.93 (t, 7= 8.6 Hz, 2H), 5.76 (dq, 7=9.9, 6.2 Hz, 1H), 4.55 (p, 7= 7.2 Hz, 1H), 4.05 (d,7= 9.8 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.23 (d,7=6.2 Hz, 3H), 0.97 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) 6 172.17, 168.91, 162.28, 161.59 (d, 7= 245.0 Hz), 159.44, 146.64, 141.48, 141.04, 137.47, 137.16 (d, 7= 3.4 Hz), 129.60 (d, 7= 7.9 Hz), 128.84, 128.02, 127.02, 115.28 (d, 7= 21.1 Hz), 109.74, 73.24, 57.00, 56.28, 47.83, 20.75, 19.22, 18.02.
449
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
549 eX (Thin film) 3380, 2983, 1770, 1735, 1676, 1507, 1451, 1436, 1310, 1201, 1175, 1046, 908, 816, 731 ESIMS m/z 509.1 ([M+H]+) 1H NMR (500 MHz, CDCh) δ 8.39 (s, 1H), 8.32 (d,/ = 5.5 Hz, 1H), 7.28-7.21 (m, 2H), 7.14 (d, J= 8.2 Hz, 2H), 7.09 (d,/= 7.9 Hz, 2H), 6.99 (d,/= 5.5 Hz, 1H), 6.95 - 6.89 (m, 2H), 5.74 (dq,/= 10.0,6.2 Hz, 1H), 4.58-4.50 (m, 1H), 4.00 (d,/= 10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.29 (s, 3H), 1.23 (d,/= 6.1 Hz, 3H), 0.97 (d,/= 7.1 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.18, 168.91, 162.27, 161.54 (d,/= 245.1 Hz), 159.44, 146.63, 141.50, 138.06, 137.48 (d,/ = 3.6 Hz), 136.65, 129.49 (d,/= 8.3 Hz), 127.86, 115.24 (d,/= 21.3 Hz), 109.73, 73.30, 56.66, 56.28, 47.83, 20.98, 20.75, 19.22, 18.02.
450
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (Y, 13c, 19f)
550 4s S' Y (Thin film) 3380, 2984, 1770, 1737, 1676, 1503, 1452, 1310, 1200, 1175, 1148, 1048, 907, 731 ESIMS m/z 513.2 ([M+H]+) 3H NMR (400 MHz, CDCh) δ 8.39 (d, J= 8.1 Hz, 1H), 8.32 (d, J= 5.5 Hz, 1H), 7.34 -7.22 (m, 5H), 7.20-7.14 (m, 1H), 6.99 (d, 7= 5.5 Hz, 1H), 6.85 - 6.74 (m, 2H), 5.80 (dtd,7=9.9, 7.3,6.7, 5.4 Hz, 1H), 4.55 (dt, 7= 8.1,7.1Hz, 1H), 4.41 (d,7 = 10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.27 (d,7=6.1 Hz, 3H), 0.92 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.13, 168.91, 162.27, 162.03 (dd, 7= 168.8, 12.1 Hz), 160.96159.14 (m), 159.43, 146.64, 141.50, 140.06, 137.46, 129.88 (dd, 7= 9.6, 5.6 Hz), 128.60, 128.27, 126.99, 124.68- 124.00 (m), 111.60 (dd, 7= 21.3, 3.6 Hz), 109.72, 104.55- 103.34 (m), 72.51, 56.28, 49.35, 47.80, 20.75, 18.92, 17.92.
451
2019201931 20 Mar 2019
Cmpd. No. R^g^ Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
551 X X X (Thin film) 3384, 2983, 1771, 1737, 1677, 1502, 1452, 1310, 1201, 1175, 1148, 1049, 966, 908, 732 ESIMS m/z 527.2 ([M+H]+) 1H NMR (400 MHz, CDCh) 6 8.40 (s, 1H), 8.32 (d,7= 5.5 Hz, 1H), 7.25-7.16 (m, 3H), 7.05 (d, 7= 7.9 Hz, 2H), 6.99 (d, 7= 5.5 Hz, 1H), 6.84-6.73 (m, 2H), 5.77 (dtd, 7=9.5, 6.5,5.2 Hz, 1H), 4.59-4.51 (m, 1H), 4.38 (d, 7= 9.8 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.26 (s, 3H), 1.25 (d,7 = 6.2 Hz, 3H), 0.96 (d,7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.12, 168.92, 162.78- 159.09 (m), 146.64, 141.53, 137.46, 136.96, 136.56, 129.88 (d, 7= 5.7 Hz), 129.24, 128.16, 124.64 (d, 7= 15.0 Hz), 111.52 (d,7 = 20.8 Hz), 109.71, 104.49 - 103.84 (m), 72.59, 56.28, 48.90, 47.84, 20.96, 20.75, 18.92, 18.00.
452
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
552 A A A (Thin film) 3384, 2985, 1770, 1737, 1676, 1503, 1201, 1175, 1160, 1148, 966, 847, 825, 811, 732 ESIMS m/z 531.2 ([M+H]+) XH NMR (400 MHz, CDCh) δ 8.37 (d, J= 6.0 Hz, 1H), 8.32 (d, J= 5.4 Hz, 1H), 7.28 -7.18(m, 3H), 7.00 (d,7= 5.5 Hz, 1H), 6.97-6.90 (m, 2H), 6.86-6.75 (m, 2H), 5.76 (dtd,7=9.7, 6.5,5.2 Hz, 1H), 4.62 - 4.48 (m, 1H), 4.39 (d, J= 9.8 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.26 (d, 7= 6.1 Hz, 3H), 1.00 (d, 7= 7.2 Hz, 3H). 13CNMR(126 MHz, CDCh) δ 172.05, 168.91, 163.09- 159.02 (m), 146.63, 141.42, 137.50, 135.78, 129.82 (d, 7= 8.2 Hz), 124.23 (d,7= 11.3 Hz), 115.42 (d, 7= 21.3 Hz), 111.98- 111.29 (m), 109.77, 104.80- 103.42 (m), 72.42, 56.30, 48.69, 47.81, 20.75, 18.93, 18.00.
453
2019201931 20 Mar 2019
Cmpd. No. Π) MP (°C) IR (cm'1) MASS NMR (¾ 13C, 19F)
553 <S· ss y SNi HRMS-ESI (m/z) ([M+H]+) calcd for C28H30FN2O6, 509.2088; found, 509.2074 1H NMR (400 MHz, CDCh) 6 8.41 (d, 7= 7.4 Hz, 1H), 8.31 (d, 7= 5.4 Hz, 1H), 7.32 -7.20(m, 4H), 7.19-7.11 (m, 1H), 7.12 - 7.02 (m, 2H), 6.98 (d, 7= 5.5 Hz, 1H), 6.90 (dd, 7=9.6, 8.1 Hz, 1H), 5.76 (dq, 7= 10.0,6.2 Hz, 1H), 4.59 - 4.45 (m, 1H), 3.99 (d, 7= 10.1 Hz, 1H), 3.88 (s, 3H), 2.37 (s, 3H), 2.22 (d, 7= 2.0 Hz, 3H), 1.23 (d, 7= 6.1 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-120.17.
554 OS y ''N HRMS-ESI (m/z) ([M+H]+) calcd for C29H31F2N2O7, 557.2099; found, 557.2091 1H NMR (400 MHz, CDCh) 6 8.40 (s, 1H), 8.31 (d,7= 5.4 Hz, 1H), 7.32 - 7.23 (m, 1H), 7.11-7.01 (m, 2H), 6.99 (d, 7= 5.5 Hz, 1H), 6.88 (t, 7= 9.3 Hz, 1H), 6.58 (td, 7=8.3, 2.5 Hz, 1H), 6.52 (dd, 7 = 10.9, 2.5 Hz, 1H), 5.74 (dq, 7= 10.1,6.2 Hz, 1H), 4.55 (dq, 7= 8.1, 7.2 Hz, 1H), 4.46 (d, 7= 10.1 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 2.38 (s, 3H), 2.21 (d, 7= 1.9 Hz, 3H), 1.20 (d,7= 6.1Hz, 3H), 0.99 (d,7=7.1 Hz, 3H). 19F NMR (376 MHz, CDCh) δ-113.46, -120.45.
*Cmpd. No. - Compound Number
454
2019201931 20 Mar 2019
Table 3. Biological Testing Rating Scale
Rating Table for Fungal Pathogens
% Control Rating
> 80 A
<80 B
Not Tested C
No Activity Observed in the Reported Assay D
Table 4. Biological Activity - PUCCRT and SEPTTR Disease Control in High and Low Volume Applications
HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEP! rTR* PUCCRT* SEP! rTR*
Cmpd. No. 1DP* 3DC* 1DP* 3DC* 1DP* 3DC* 1DP* 3DC*
89 C C C C C C C C
90 A A A A C C C C
91 A B A D C C C C
92 A A A A A B A A
93 B D A B C C C C
95 C C C C C C C C
96 A A A A c C c c
97 B D A A c C c c
98 A A A A c C c c
99 A B A A c C c c
100 A A A A c C c c
101 D D B D c c c c
102 B D B B c c c c
103 A B A A c c c c
104 A D B A c c c c
105 A A A A c c c c
106 A D A A c c c c
107 A B A A c c c c
109 B D D B c c c c
455
2019201931 20 Mar 2019
110 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
A D A A C C C C
111 B D B A C C C C
112 D D B B C c C c
113 A B A B C c C c
114 A A A A C c C c
115 B D A A C c C c
116 B D B B c c C c
117 A B A A c c C c
118 A A B A c c C c
119 D D A B c c C c
120 A B A A c c c c
121 A B A A c c c c
122 D D B B c c c c
123 B D B A c c c c
124 A A A A c c c c
125 A A A A c c c c
127 B D B D c c c c
128 B D A B c c c c
129 A B A A c c c c
130 B D A D c c c c
131 A D A A c c c c
132 A B A A c c c c
133 A A A A c c c c
135 B D B D c c c c
136 A B A B c c c c
137 A B A A c c c c
138 C C C C D B A B
139 C C C C A A A A
140 c C c c A B A A
141 c C c c A A A A
142 c C c c A A A A
143 c C c c B D D B
144 c C c c B B B B
145 c C c c A A A A
146 c C c c A A A A
147 c C c c B B B A
148 c C c c A A A A
456
2019201931 20 Mar 2019
149 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
C c c c B B A A
150 C c c c A A A A
152 C c c c B B A A
153 C c c c B B A A
155 C c c c A A A A
156 C c c c A A A A
157 C c c c A A A A
158 c c c c A A A A
159 c c c c A A A A
160 c c c c A B A A
161 c c c c D D B A
162 c c c c D D D B
163 c c c c B D B A
164 c c c c D D B D
165 c c c c A B A A
166 c c c c B D B B
167 c c c c A A A A
168 c c c c A B A A
169 c c c c A B A A
170 c c c c B B B B
171 c c c c A A A A
173 c c c c A B A A
174 c c c c A B A A
175 c c c c A A A A
176 c c c c A A A A
178 c c c c B D A A
179 c c c c B D A A
180 c c c c D D B D
181 c c c c D D B B
182 c c c c D B D B
183 c c c c A A A B
184 c c c c A A A A
185 c c c c A B A A
186 c c c c B D A B
187 c c c c A B B B
188 c c c c A B A A
189 c c c c A B A A
457
2019201931 20 Mar 2019
190 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
C c c c B D B B
191 C c c c A A A A
192 C c c c A A A A
193 C c c c B D A A
194 C c c c A B A A
195 C c c c A B A B
196 C c c c D D A B
197 c c c c A A A A
198 c c c c A B A A
199 c c c c A A A A
201 c c c c B D A A
202 c c c c D D A A
203 c c c c A B A A
204 c c c c A A A A
206 c c c c A B A A
207 c c c c D D A A
208 c c c c A B A A
209 c c c c A B A A
210 c c c c A B A A
211 c c c c A A A A
212 c c c c A A A A
213 c c c c B B A A
214 c c c c D D D D
215 c c c c A D A A
216 c c c c A B A B
217 c c c c A B A A
218 c c c c A B A A
219 c c c c A D A A
220 c c c c A B A A
221 c c c c B D B A
222 c c c c A D A A
223 c c c c B D B B
224 c c c c B D A A
225 c c c c D D D D
228 c c c c C C C C
229 c c c c D D D B
230 c c c c D D D D
386 B D B D C C C C
387 A B A B C C C C
458
2019201931 20 Mar 2019
388 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
B B A A C c c c
389 A D D D C c c c
390 A B A D C c c c
391 A A A A C c c c
392 A B A D C c c c
393 C C C C C c c c
394 B D A B C c c c
395 A A A A c c c c
396 A A A A c c c c
397 A D A A c c c c
398 B B B B c c c c
399 A A A A c c c c
400 A A A A c c c c
401 A B A A c c c c
402 A B A B c c c c
403 A B A A c c c c
404 A A A A c c c c
405 A A A A c c c c
406 A A A A c c c c
407 A A A A c c c c
408 A B A A c c c c
409 A D A A c c c c
410 B D B B c c c c
411 A B A A c c c c
412 C C C C c c c c
413 A B A A c c c c
414 B D A B c c c c
415 A B A A c c c c
416 A D A B c c c c
417 A D B B c c c c
418 A A A A c c c c
419 B D B B c c c c
420 B D B D c c c c
421 D D D D c c c c
422 D D B D c c c c
423 A A A A c c c c
424 A B A A c c c c
425 A A A A c c c c
426 A D A A c c c c
459
2019201931 20 Mar 2019
427 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
B D B B C c c c
428 B D B A C c c c
429 B D B B C c c c
430 A B A A C c c c
431 A A A A C c c c
432 B A A A C c c c
433 A A A A C c c c
434 A A A A c c c c
435 A A A A c c c c
436 A A A A c c c c
437 A A A A c c c c
438 A A A A c c c c
439 A A A A c c c c
440 A A A A c c c c
441 A B A A c c c c
442 A A A A c c c c
443 A A A A c c c c
444 A A A A c c c c
445 A B A A c c c c
446 A B A A c c c c
447 A A A A c c c c
448 A A A A c c c c
449 A A A A c c c c
450 A B A A c c c c
451 A A A A c c c c
452 A A A A c c c c
453 A A A A c c c c
454 A A A A c c c c
455 A A A A c c c c
456 A A A A c c c c
457 A A A A c c c c
458 A A A A c c c c
459 A A A A c c c c
460 A A A A c c c c
461 A A A A c c c c
462 C C C C D D D B
463 C C C C D D D B
460
2019201931 20 Mar 2019
464 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
C c c c A A A A
465 C c c c B D D D
466 C c c c B D A B
467 C c c c B B A B
468 C c c c A B A A
469 C c c c B D D D
470 C c c c B B B B
471 c c c c A B A A
472 c c c c A A A A
473 c c c c B B A A
474 c c c c B D A A
475 c c c c A A A A
476 c c c c A A A A
477 c c c c B B A A
478 c c c c B D A B
479 c c c c D D A B
480 c c c c D B D D
481 c c c c B B B A
482 c c c c B A B A
483 c c c c B B A B
484 c c c c A B A B
485 c c c c A A A A
486 c c c c A B A A
487 c c c c A A B A
488 c c c c A B A A
489 c c c c A A A A
490 c c c c A B A A
491 c c c c A B A A
492 c c c c B B A A
493 c c c c B B B B
494 c c c c B B B B
495 c c c c B B B D
496 c c c c A B A A
497 c c c c A B A B
498 c c c c A B A A
499 c c c c B D A A
500 c c c c A B A A
501 c c c c B B A B
461
2019201931 20 Mar 2019
502 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPTTR* PUCCRT* SEPTTR*
C c c c A B B D
503 C c c c A B A A
504 C c c c A D B B
505 C c c c B D B D
506 C c c c D D D D
507 C c c c D D B D
508 C c c c A A A A
509 c c c c A B B B
510 c c c c A A A A
511 c c c c D B D D
512 c c c c D D D D
513 c c c c B D D D
514 c c c c D D D D
515 c c c c D D D D
516 c c c c A A A A
517 c c c c A B D B
518 c c c c A A A A
519 c c c c B B A B
520 c c c c D D D D
521 c c c c B B A B
522 c c c c B D A B
523 c c c c A A A A
524 c c c c A A A A
525 c c c c A A A A
526 c c c c A B A A
527 c c c c A B A A
528 c c c c A B A A
529 c c c c A B A A
530 c c c c A D A A
531 c c c c A A A A
532 c c c c A A A A
533 c c c c A A A A
534 c c c c A B A A
535 c c c c A A A A
536 c c c c A B A A
537 c c c c A A A A
538 c c c c A B A A
539 c c c c A B A A
540 c c c c A B A A
462
2019201931 20 Mar 2019
541 HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEPr c 'TR* c PUCCRT* SEPr A 'TR* A
C c A B
542 C c c c A B A A
543 C c c c A B A A
544 C c c c A A A A
545 C c c c A A A A
546 C c c c A A A A
547 C c c c A A A A
548 c c c c A A A A
549 c c c c A A A A
550 c c c c A A A A
551 c c c c A A A A
552 c c c c A A A A
553 c c c c A A A A
554 c c c c A A A A
Cmpd. No. - Compound Number
PUCCRT - Wheat Brown Rust (Puccinia triticina) SEPTTR - Wheat Leaf Blotch (Zymoseptoria tritici) 1DP - 1 Day Protectant
3DC - 3 Day Curative g/H - Grams Per Hectare ppm - Parts Per Million
Table 5. Biological Activity - Disease Control at 100 ppm
ALTESO* CERCBE* COLLLA* LEPTNO*
Cmpd. No. 1DP*
92 B A A A
139 B A A A
140 A A A A
141 B A A A
142 A A A A
145 A A A A
146 A A A A
148 B A A A
150 A A A A
167 A A A A
171 B A A A
463
2019201931 20 Mar 2019
ALTESO* CERCBE* COLLLA* LEPTNO*
Cmpd. No. 1DP*
174 B A A A
176 B A A A
199 A A A A
204 A A A A
464 B A A A
468 A A A A
472 B A A A
475 B A A A
524 A A A A
528 B A A A
532 B A A A
Cmpd. No. - Compound Number
ALTESO - Tomato Early Blight (Alternaria solani)
CERCBE - Leaf Spot of Sugar Beets (Cercospora beticola) COLLLA - Cucumber Anthracnose (Colletotricum lagenarium) LEPTNO - Wheat Glume Blotch (Leptosphaeria nodoruni)
1DP - 1 Day Protectant
Table 6. Biological Activity - Disease Control at 100 ppm
PYRIOR* RHYNSE* VENTIN*
Cmpd. No. 1DP*
92 C A C
139 A A A
140 A C A
141 A A A
142 A A A
145 A A A
146 A A A
148 A A A
150 A A A
167 A A C
171 A A C
174 A A B
176 A A A
199 A A C
204 A A C
464 A A A
464
2019201931 20 Mar 2019
PYRIOR* RHYNSE* VENTIN*
Cmpd. No. 1DP*
468 A A A
472 A A A
475 A A B
524 A A A
528 A A A
532 C A C
Cmpd. No. - Compound Number
PYRIOR -. Rice Blast (Pyricularia oryzae) RHYNSE - Barley Scald (Rhyncosporium secalis) VENTIN - Apple Scab (Venturia inaequalis) *1DP - 1 Day Protectant
Table 7. Biological Activity - Disease Control at 25 ppm
PHAKPA*
Cmpd. No. 1DP* 3DC*
139 A B
140 B D
141 A B
142 A B
92 B B
145 A B
146 A B
148 A B
150 A A
158 A B
167 A B
169 A D
171 A B
173 B D
174 A B
175 B D
176 B B
199 A B
204 A B
207 B D
208 A B
209 A B
465
2019201931 20 Mar 2019
PHAJ ECPA*
Cmpd. No. 1DP* 3DC*
210 A D
211 A B
212 B D
213 A B
464 A A
468 A B
472 A B
475 A B
493 D D
494 D D
495 B D
496 B D
497 D D
498 A B
499 B B
500 A B
501 B B
502 B D
503 A D
504 B D
505 D D
506 D D
507 D D
508 B D
509 D D
510 B D
511 D D
512 D D
513 D D
514 D D
515 D D
516 B D
517 B D
518 B D
519 D B
520 D D
521 B D
522 B D
523 A B
466
2019201931 20 Mar 2019
PHA1 ECPA*
Cmpd. No. 1DP* 3DC*
524 A B
525 A B
526 A D
527 A B
528 A B
529 A B
530 A B
531 A B
532 A B
533 A B
534 A B
535 B D
536 A B
537 A B
538 B B
539 A B
540 A B
541 A B
542 B D
543 A B
544 A B
545 B D
546 A B
547 A B
548 A D
549 B D
550 A B
551 A B
552 A B
553 B D
554 B D
Cmpd. No. - Compound Number PH A KPA - Asian Soybean Rust (Phakopsora pachyrhizi) *1DP - 1 Day Protectant *3DC - 3 Day Curative

Claims (20)

  1. What is claimed is:
    5 1. A compound of Formula 1
    CLAIMS wherein:
    X is hydrogen or C(O)Rs;
    Y is hydrogen, C(O)R5, or Q;
    0 Qis wherein: Z is N or CH:
    Ri is hydrogen or alkyl, substituted with 0, 1 or multiple R8;
    R
  2. 2 is methyl;
    15 R3 is aryl optionally substituted with 0, 1 or multiple Rs. and bound to R12 either directly or through an oxo bridge;
    R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy;
    Rs is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple
    Rs;
    20 R<5 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
    R7 is chosen from hydrogen, -C(O)R9, or -CH2OC(O)R9;
    468
    1002492809
    2019201931 20 Mar 2019
    R8 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, each optionally substituted withO, 1, or multiple Rio;
    R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R8;
    5 Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl;
    Rn is chosen from hydrogen or alkyl, substituted with 0, 1 or multiple R8; and
    R12 is aryl optionally substituted with 0, 1 or multiple R8, and bound to R3 either directly or through an oxo bridge.
    0 2. The compound according to Claim 1, wherein X and Y are hydrogen.
  3. 3. The compound according to Claim 2, wherein Ri and Rn are independently chosen from hydrogen or alkyl.
  4. 5 4. The compound according to Claim 2, wherein R4 is H.
    5. The compound according to Claim 2, wherein Ri and Rn are independently chosen from hydrogen or alkyl, and R4 is H.
    20
  5. 6. The compound according to Claim 1, wherein X is C(O)Rs and Y is hydrogen.
  6. 7. The compound according to Claim 6, wherein Ri and Rn are independently chosen from hydrogen or alkyl.
    25
  7. 8. The compound according to Claim 6, wherein R4 is H.
  8. 9. The compound according to Claim 6, wherein Ri and Rn are independently chosen from hydrogen or alkyl, and R4 is H.
    469
    1002492809
    2019201931 20 Mar 2019
  9. 10. The compound according to Claim 1, wherein X is hydrogen and Y is Q.
  10. 11. The compound according to Claim 10, wherein Z is N.
  11. 12. The compound according to Claim 10 or 11, wherein R(, is alkoxy.
  12. 13. The compound according to any one of Claims 10 to 12, wherein R7 is hydrogen.
    0
  13. 14. The compound according to Claim 13, wherein Ri and Rn are independently chosen from hydrogen or alkyl.
  14. 15. The compound according to Claim 13, wherein R4 is H.
    5
  15. 16. The compound according to Claim 13, wherein Ri and Rn are independently chosen from hydrogen or alkyl, and R4 is H.
  16. 17. The compound according to Claim 12, wherein R7 is chosen from -C(O)R9, or
    CH2OC(O)R9.
  17. 18. The compound according to Claim 17, wherein Ri and Rn are independently chosen from hydrogen or alkyl.
  18. 19. The compound according to Claim 17, wherein R4 is H.
  19. 20. The compound according to Claim 17, wherein Ri and Rn are independently chosen from hydrogen or alkyl, and R4 is H.
    470
    1002492809
    2019201931 20 Mar 2019
  20. 21. The compound according to Claim 20, wherein R9 is chosen from -CH3, -CH2OCH2CH3, CH2CH2OCH3, CH(CH3)2, CH2CH2CH2CH3, or cyclopropyl.
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